DE112014001269B4 - Liquid crystal composition, use of the liquid crystal composition for producing a film, a polarizing plate and a liquid crystal display device, polymer material and method for producing the same - Google Patents

Abstract

A liquid crystal composition comprising:at least one species of the compound represented by the following formula (4), at least one species of the compound represented by the following formula (5), and at least one species of the compound represented by the following formula (6), wherein n1 is an integer from 3 to 6 represents, R11 represents a hydrogen atom or a methyl group, Z12 represents -CO- or -CO-CH=CH-, R12 represents a hydrogen atom, a straight-chain alkyl group with 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, represents an allyloxy group or a structure represented by the following formula (1-3) wherein Z13 represents -CO- or -CO-CH=CH-, Z14 represents-CO- or -CH=CH-CO-, each of R13 and R14 independently hydrogen atom, a straight-chain alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, an allyloxy group or a structure represented by the following formula (1-3), wherein each of n2 and n3 independently each represents an integer of 3 to 6 and each of R15 and R16 independently represents a hydrogen atom or a methyl group,-Z51-T-Sp-PFormula (1-3)wherein P represents an acrylic group or a methacrylic group,Z51-COO- represents T represents a 1,4-phenylene group and Sp represents an optionally substituted divalent aliphatic group having 2 to 6 carbon atoms, a CH2 group or two or more non-adjacent CH2 groups in the aliphatic group by -O-, -OCO-, -COO- or -OCOO- can be replaced.

Description

TECHNICAL FIELD

This invention relates to a liquid crystal composition comprising a polymerizable liquid crystal compound which is versatile for various applications represented by various optical components including an optically anisotropic film, a thermal barrier film, etc. Uses of the liquid crystal composition for producing a film, a polarizing plate and a Liquid crystal display device, a method of producing a polymer material using such a liquid crystal composition and a polymer material.

STATE OF THE ART

Liquid crystal material is used in various industrial fields including a phase difference film, a polarizing element, a selective reflection film, a color filter, an anti-reflection film, a viewing angle compensation film, holography, an alignment film, etc. In particular, a bifunctional liquid crystalline (meth)acrylate compound is extremely versatile and has been used for various applications.

However, the bifunctional liquid crystalline (meth)acrylate compound is extremely crystallizable, and therefore the bifunctional liquid crystalline (meth)acrylate compound alone or a composition of bifunctional liquid crystalline (meth)acrylate compounds is very likely to unfortunately crystallize in a coating process. It is therefore desirable to develop an additive capable of suppressing crystal deposition of the polymerizable liquid crystal compound.

As a countermeasure, it is known that mixing a main polymerizable liquid crystal compound with another polymerizable liquid crystal compound successfully lowers the melting point. Patent Literature 1 also discloses that crystallization can be suppressed even if a polymerizable liquid crystal compound having a specific molecular structure is further mixed. Patent Literature 1 describes that a bifunctional (meth)acrylate compound in which the hydroquinone nucleus having a C ₄ or longer substituent and further having a C ₅ or longer substituent is added to a liquid crystal material. Patent Literature 1 discloses that the crystallization of the compound is successfully suppressed even when it is supercooled from the liquid crystal state to room temperature without deteriorating the properties including the orientation ability and the hardenability. However, Patent Literature 1 only describes bifunctional polymerizable liquid crystal compounds, and is not satisfactory because the bifunctional polymerizable liquid crystal compound has a molecular structure with poor synthesis suitability, which is required to synthesize the core part separately.

Although not mentioned regarding the suppression of crystallization, Non-Patent Literature 1, on the other hand, describes a monofunctional polymerizable liquid crystal compound which is a benzoate ester of a substituted hydroquinone nucleus. The monofunctional polymerizable liquid crystal compound described in Non-Patent Literature 1 was a compound configured by two different benzoate esters of methyl hydroquinone with a benzoate ester having a (meth)acrylate group on one side and a benzoate ester having a C ₆ alkoxy group on the other side. According to Non-Patent Literature 1, a cholesteric liquid crystal composition is prepared using a liquid crystal composition containing 95 mass% of the monofunctional polymerizable liquid crystal compound described above, 5 mass% of a chiral agent and a polymerization initiator, so there is no suggestion in Non-Patent Literature 1 reported the use of the monofunctional polymerizable liquid crystal compound as an additive to suppress crystallization.

Although not mentioned with regard to the suppression of crystallization, Patent Literature 2 also describes a method for producing a monofunctional polymerizable liquid crystal compound having a substituted hydroquinone core as any mixture with a bifunctional polymerizable liquid crystal compound. The monofunctional polymerizable liquid crystal compound contained in the arbitrary mixture described in Patent Literature 2 was a compound formed by two different benzoate esters of methyl hydroquinone with a benzoate ester having a (meth)acrylate group on one side and a benzoate ester having a C ₆ alkoxy group as side chain was configured on the other side. Furthermore, in Patent Literature 2, there is neither a disclosure nor a suggestion as to whether the compound described in the literature exhibits a suppressing effect on crystallization.

Patent Literature 3 describes a liquid crystal composition that can be successfully prevented from crystallizing during storage at low temperatures by containing three or more species of a phenylenebis(4-alkylbenzenecarboxylate) compound. It is described that a particularly great suppression effect on crystallization is obtained when at least one species of these three or more species of a phenylenebis(4-alkylbenzenecarboxylate) compound is an asymmetric compound having different alkyl groups.

QUOTE LIST

PATENT LITERATURE

• [Patent Literature 1] JP 2009- 184 974 A
• [Patent Literature 2] JP 2002- 536 529 A
• [Patent Literature 3] JP H09- 279 144 A

[Non-patent literature 1] Molecular crystals and Liquid Crystals (2010), 530, 169-174

SUMMARY OF THE INVENTION

TECHNICAL TASK

It is known that the melting point of a main polymerizable liquid crystal is generally lowered when another polymerizable liquid crystal compound is mixed as described above. However, there is little knowledge about adding what kind of molecular structure of the liquid crystal compound to the main polymerizable liquid crystal exhibits the suppressing effect on crystallization, so the effect is difficult to predict.

Non-Patent Literature 1 describes a method for producing a cholesteric liquid crystal film using a liquid crystal composition containing 95% by mass of the above-described monofunctional polymerizable liquid crystal compound and 5% by mass of a chiral agent. However, Non-Patent Literature 1 does not suggest that the monofunctional polymerizable liquid crystal compound is used as an additive for suppressing crystallization.

Patent Literature 1 only describes the bifunctional polymerizable liquid crystal compound, which, however, remains unsatisfactory in that the compound is troublesome in suitability for synthesis because its molecular structure requires separate synthesis of the core.

Whether or not the compound disclosed therein has a suppressing effect on crystallization is also neither disclosed nor suggested by Patent Literature 2.

In this situation, the present inventors used the monofunctional polymerizable liquid crystal compound described in Non-Patent Literature 1 as an additive and tested the crystallization suppressing effect, but found that the crystallization suppressing effect was poor.

The present inventors also conducted a similar experiment on the crystallization suppressing effect using the monofunctional polymerizable liquid crystal compound described in Patent Literature 2 as an additive to find that the crystallization suppressing effect was also poor.

The present inventors further conducted a similar experiment on the crystallization suppressing effect using the liquid crystal composition described in Patent Literature 3 to find poor crystallization suppressing effect. An improved suppression effect on crystallization is therefore required.

It is therefore an object of the present invention to achieve the above objects and to provide a liquid crystal composition having a strong crystallization suppressing effect.

SOLUTION OF THE TASK

After extensive studies to solve the above-mentioned objects, the present inventors have found that the object of this invention could be successfully achieved by using a later-described liquid crystal composition containing a compound represented by the formula (4), a compound represented by the formula (5 ) and a compound represented by formula (6).

Preferably, a polymerizable liquid crystal compound having one (meth)acrylate group, a liquid crystal compound having no (meth)acrylate group, and a polymerizable liquid crystal compound having two (meth)acrylate groups are used. Here, the polymerizable liquid crystal compound having a (meth)acrylate group has an asymmetrical structure, and the length of the substituent substituted on the phenyl group on the side not containing a (meth)acrylate group therein is controlled to be shorter than the length in the connections particularly disclosed in Patent Literature 2 and Non-Patent Literature 1. In addition, a liquid crystal compound having a skeleton similar to the skeleton of the polymerizable liquid crystal compound having a (meth)acrylate group and not having a (meth)acrylate group is used. The inventors here have also found that by using such a liquid crystal compound, the crystallization suppressing effect can be further improved.

• [1] Flüssigkristallzusammensetzung umfassend mindestens eine Spezies der durch die folgende Formel (4) dargestellten Verbindung, mindestens eine Spezies der durch die folgende Formel (5) dargestellten Verbindung und mindestens eine Spezies der durch die folgende Formel (6) dargestellten Verbindung
  
  worin n1 eine ganze Zahl 3 bis 6 darstellt, R¹¹ ein Wasserstoffatom oder eine Methylgruppe darstellt, Z¹² -CO- oder -CO-CH=CH- darstellt, R¹² eine Wasserstoffatom, eine geradkettige Alkylgruppe mit 1 bis 4 Kohlenstoffatomen, eine Methoxygruppe, eine Ethoxygruppe, eine Phenylgruppe, eine Acryloylaminogruppe, eine Methacryloylaminogruppe, eine Allyloxygruppe oder eine durch die folgende Formel (1-3) dargestellte Struktur darstellt
  
  worin Z¹³ -CO- oder -CO-CH=CH- darstellt, Z¹⁴ -CO- oder -CH=CH-CO- darstellt, jede von R¹³ und R¹⁴ unabhängig voneinander ein Wasserstoffatom, eine geradkettige Alkylgruppe mit 1 bis 4 Kohlenstoffatomen, eine Methoxygruppe, eine Ethoxygruppe, eine Phenylgruppe, eine Acryloylaminogruppe, eine Methacryloylaminogruppe, eine Allyloxygruppe oder eine durch die folgende Formel (1-3) darstellte Struktur darstellt,
  
  worin jedes von n2 und n3 unabhängig voneinander eine ganze Zahl von 3 bis 6 darstellt und jedes von R¹⁵ und R¹⁶ unabhängig voneinander ein Wasserstoffatom oder eine Methylgruppe darstellt, -Z⁵¹-T-Sp-P Formel (1-3) worin P eine Acrylgruppe oder eine Methacrylgruppe darstellt, Z⁵¹ -COO- darstellt, T eine 1,4-Phenylengruppe darstellt und Sp eine gegebenenfalls substituierte divalente aliphatische Gruppe mit 2 bis 6 Kohlenstoffatomen darstellt, eine CH₂-Gruppe oder zwei oder mehrere nicht benachbarte CH₂-Gruppen in der aliphatischen Gruppe durch -O-, -OCO-, -COO- oder -OCOO- ersetzt sein können.
• [2] Flüssigkristallzusammensetzung gemäß [1], worin mindestens zwei von R¹², R¹³ und R¹⁴ denselben Substituenten darstellen.
• [3] Flüssigkristallzusammensetzung gemäß [1] oder [2], worin n1 4 ist.
• [4] Flüssigkristallzusammensetzung gemäß irgendeinem von [1] bis [3], worin jedes von R¹¹, R¹⁵ und R¹⁶ ein Wasserstoffatom darstellt.
• [5] Flüssigkristallzusammensetzung gemäß irgendeinem von [1] bis [4], worin jedes von Z¹², Z¹³ und Z¹⁴ -CO- darstellt.
• [6] Flüssigkristallzusammensetzung gemäß irgendeinem von [1] bis [5], worin jedes von R¹², R¹³ und R¹⁴ unabhängig voneinander eine Methylgruppe, eine Ethylgruppe, eine Methoxygruppe, eine Ethoxygruppe, eine Phenylgruppe, eine Acryloylaminogruppe, eine Methacryloylaminogruppe, eine Allyloxygruppe oder eine durch die folgende Formel (1-3) dargestellte Struktur darstellt: -Z⁵¹-T-Sp-P Formel (1-3) worin P eine Acrylgruppe oder eine Methacrylgruppe darstellt, Z⁵¹ -COO- darstellt, T eine 1,4-Phenylengruppe darstellt und Sp eine gegebenenfalls substituierte divalente aliphatische Gruppe mit 2 bis 6 Kohlenstoffatomen darstellt, eine CH₂-Gruppes oder zwei oder mehrere nicht benachbarte CH₂-Gruppen in der aliphatischen Gruppe durch -O-, -OCO-, -COO- oder -OCOO- ersetzt sein können.
• [7] Flüssigkristallzusammensetzung gemäß irgendeinem von [1] bis [6], worin jedes von R¹², R¹³ und R¹⁴ eine Phenylgruppe darstellt.
• [8] Flüssigkristallzusammensetzung gemäß irgendeinem von [1] bis [7], die 3 bis 50 Masse-% der durch die Formel (4) dargestellten Verbindung und 0,01 bis 10 Masse-% der durch die Formel (5) dargestellten Verbindung, bezogen auf die durch die Formel (6) dargestellten Verbindung, enthält.
• [9] Flüssigkristallzusammensetzung gemäß irgendeinem von [1] bis [8], die mindestens eine Spezies eines Polymerisationsinitiators enthält.
• [10] Flüssigkristallzusammensetzung gemäß irgendeinem von [1] bis [9], die mindestens eine Spezies einer chiralen Verbindung enthält.
• [11] Verfahren zur Herstellung eines Polymermaterials, umfassend das Polymerisieren einer in irgendeinem der von [1] bis [10] beschriebenen Flüssigkristallzusammensetzung.
• [12] Verfahren zur Herstellung eines Polymermaterials gemäß [11], worin die Polymerisation durch Bestrahlung mit Ultraviolettstrahlung erzielt wird.
• [13] Polymermaterial, erhältlich durch Polymerisieren der in irgendeinem von [1] bis [10] beschriebenen Flüssigkristallzusammensetzung.
• [14] Verwendung der Flüssigkristallzusammensetzung gemäß irgendeinem von [1] bis [10] zur Herstellung eines Films, der mindestens eine Spezies eines enthält, das durch Polymerisieren der Flüssigkristallzusammensetzung erhältlich ist.
• [15] Verwendung der Flüssigkristallzusammensetzung gemäß irgendeinem von [1] bis [10] zur Herstellung eines Films umfassend eine optisch anisotrope Schicht, die durch Fixieren einer Ausrichtung der in der Flüssigkristallzusammensetzung enthaltenen Flüssigkristallverbindungen konfiguriert ist.
• [16] Verwendung gemäß [15], wobei die optisch anisotrope Schicht durch Fixieren einer cholesterischen Ausrichtung der Flüssigkristallverbindungen konfiguriert ist.
• [17] Verwendung gemäß [16], wobei der Film eine selektive Reflexionseigenschaft aufweist.
• [18] Verwendung gemäß [16] oder [17], wobei der Film eine selektive Reflexionseigenschaft im Infrarotwellenlängenbereich aufweist.
• [19] Verwendung gemäß [15], wobei die optisch anisotrope Schicht durch Fixieren einer homogenen Ausrichtung der Flüssigkristallverbindung konfiguriert ist.
• [20] Verwendung gemäß [15], wobei die optisch anisotrope Schicht durch Fixieren einer homeotropen Ausrichtung der Flüssigkristallverbindungen konfiguriert ist.
• [21] Verwendung der Flüssigkristallzusammensetzung gemäß irgendeinem von [1] bis [10] zur Herstellung einer polarisierenden Platte, die einen Film und einen Polarisationsfilm umfasst, wobei der Film eine optisch anisotrope Schicht umfasst, die durch Fixieren einer homogenen oder homeotropen Ausrichtung der in der Flüssigkristallzusammensetzung enthaltenen Flüssigkristallverbindungen konfiguriert ist.
• [22] Verwendung der Flüssigkristallzusammensetzung gemäß irgendeinem von [1] bis [10] zur Herstellung einer Flüssigkristallanzeigevorrichtung umfassend eine polarisierende Platte, die einen Film und einen Polarisationsfilm umfasst, wobei der Film eine optisch anisotrope Schicht umfasst, die durch Fixieren einer homogenen oder homeotropen Ausrichtung der in der Flüssigkristallzusammensetzung enthaltenen Flüssigkristallverbindungen konfiguriert ist.

In particular, the above task was solved by the following [1], preferably the following [2] to [22].

• [1] Liquid crystal composition comprising at least one species of the compound represented by the following formula (4), at least one species of the compound represented by the following formula (5), and at least one species of the compound represented by the following formula (6).
  
  where n1 represents an integer 3 to 6, R ¹¹ represents a hydrogen atom or a methyl group, Z ¹² represents -CO- or -CO-CH=CH-, R ¹² represents a hydrogen atom, a straight-chain alkyl group with 1 to 4 carbon atoms, a methoxy group , an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, an allyloxy group or a structure represented by the following formula (1-3).
  
  wherein Z ¹³ represents -CO- or -CO-CH=CH-, Z ¹⁴ represents -CO- or -CH=CH-CO-, each of R ¹³ and R ¹⁴ independently represents a hydrogen atom, a straight chain alkyl group with 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, an allyloxy group or a structure represented by the following formula (1-3),
  
  wherein each of n2 and n3 independently represents an integer from 3 to 6 and each of R ¹⁵ and R ¹⁶ independently represents a hydrogen atom or a methyl group, -Z ⁵¹ -T-Sp-P Formula (1-3) where P represents an acrylic group or a methacrylic group, Z ⁵¹ represents -COO-, T represents a 1,4-phenylene group and Sp represents an optionally substituted divalent aliphatic group having 2 to 6 carbon atoms, a CH ₂ group or two or more non-adjacent CH ₂ -Groups in the aliphatic group can be replaced by -O-, -OCO-, -COO- or -OCOO-.
• [2] Liquid crystal composition according to [1], wherein at least two of R ¹² , R ¹³ and R ¹⁴ represent the same substituent.
• [3] Liquid crystal composition according to [1] or [2], wherein n1 is 4.
• [4] A liquid crystal composition according to any one of [1] to [3], wherein each of R ¹¹ , R ¹⁵ and R ¹⁶ represents a hydrogen atom.
• [5] A liquid crystal composition according to any one of [1] to [4], wherein each of Z ¹² , Z ¹³ and Z ¹⁴ represents -CO-.
• [6] A liquid crystal composition according to any one of [1] to [5], wherein each of R ¹² , R ¹³ and R ¹⁴ independently represents a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, a allyloxy group or a structure represented by the following formula (1-3): -Z ⁵¹ -T-Sp-P Formula (1-3) where P represents an acrylic group or a methacrylic group, Z ⁵¹ represents -COO-, T represents a 1,4-phenylene group and Sp represents an optionally substituted divalent aliphatic group having 2 to 6 carbon atoms, a CH ₂ group or two or more non-adjacent ones CH ₂ groups in the aliphatic group can be replaced by -O-, -OCO-, -COO- or -OCOO-.
• [7] A liquid crystal composition according to any one of [1] to [6], wherein each of R ¹² , R ¹³ and R ¹⁴ represents a phenyl group.
• [8] Liquid crystal composition according to any one of [1] to [7], which contains 3 to 50 mass% of the compound represented by formula (4) and 0.01 to 10 mass% of the compound represented by formula (5), based on the compound represented by formula (6).
• [9] Liquid crystal composition according to any one of [1] to [8], containing at least one species of polymerization initiator.
• [10] A liquid crystal composition according to any one of [1] to [9] containing at least one species of a chiral compound.
• [11] A method for producing a polymer material, comprising polymerizing a liquid crystal composition described in any of [1] to [10].
• [12] A method for producing a polymer material according to [11], wherein polymerization is achieved by irradiation with ultraviolet radiation.
• [13] Polymer material obtainable by polymerizing the liquid crystal composition described in any of [1] to [10].
• [14] Use of the liquid crystal composition according to any one of [1] to [10] for producing a film containing at least one species obtainable by polymerizing the liquid crystal composition.
• [15] Use of the liquid crystal composition according to any one of [1] to [10] for producing a film comprising an optically anisotropic layer configured by fixing an orientation of the liquid crystal compounds contained in the liquid crystal composition.
• [16] Use according to [15], wherein the optically anisotropic layer is configured by fixing a cholesteric orientation of the liquid crystal compounds.
• [17] Use according to [16], wherein the film has a selective reflection property.
• [18] Use according to [16] or [17], wherein the film has a selective reflection property in the infrared wavelength range.
• [19] Use according to [15], wherein the optically anisotropic layer is configured by fixing a homogeneous orientation of the liquid crystal compound.
• [20] Use according to [15], wherein the optically anisotropic layer is configured by fixing a homeotropic orientation of the liquid crystal compounds.
• [21] Use of the liquid crystal composition according to any one of [1] to [10] for producing a polarizing plate comprising a film and a polarizing film, the film comprising an optically anisotropic layer obtained by fixing a homogeneous or homeotropic orientation of the in the Liquid crystal compounds containing liquid crystal composition is configured.
• [22] Use of the liquid crystal composition according to any one of [1] to [10] for producing a liquid crystal display device comprising a polarizing plate comprising a film and a polarizing film, the film comprising an optically anisotropic layer formed by fixing a homogeneous or homeotropic orientation of the liquid crystal compounds contained in the liquid crystal composition.

ADVANTAGEOUS EFFECTS OF THE INVENTION

According to the present invention, it is now possible to provide a polymerizable liquid crystal compound which is easily synthesized and exhibits high performance in suppressing crystallization.

DESCRIPTION OF EMBODIMENTS

This invention is described in detail below. An explanation of the constitutive features will occasionally be made using representative embodiments or specific examples of this invention, to which this invention is in no way limited. In this invention, all numerical ranges expressed using "to" with preceding and following digits are defined to include these digits as lower and upper limits.

In this description (meth)acrylate refers to a group consisting of acrylate and methacrylate.

<First Embodiment of the Invention>

[Liquid crystal composition]

The liquid crystal composition of this invention contains at least one species of a compound represented by the following formula (4), at least one species of a compound represented by the following formula (5), and at least one species of a compound represented by the following formula (6).

The liquid crystal composition of this invention exhibits a strong crystallization suppressing effect. The liquid crystal composition of this invention can be easily synthesized.

The individual compounds contained in the liquid crystal composition of this invention will be explained.

[Compound represented by formula (4)]

The compound used for the liquid crystal composition of this invention is a compound represented by the following formula (4), and preferably a polymerizable liquid crystal compound having a (meth)acrylate group represented by the following formula (4).

(In formula (4), n1 represents an integer from 3 to 6,
R ¹¹ represents a hydrogen atom or a methyl group,
Z ¹² represents -CO- or -CO-CH=CH-,
R ¹² represents a hydrogen atom, a straight-chain alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, an allyloxy group or a structure represented by the following formula (1-3): Z ⁵¹ -T-Sp-P Formula (1-3)
(In formula (1-3), P represents an acrylic group or a methacrylic group,
Z ⁵¹ represents -COO-,
T represents 1,4-phenylene, Sp represents an optionally substituted divalent aliphatic group with 2 to 6 carbon atoms, in which one CH ₂ group or two or more non-adjacent CH ₂ groups in the aliphatic group are replaced by -O-, - OCO, -COO- or -OCOO- can be replaced)).
n1 represents an integer from 3 to 6 and particularly preferably 3 or 4.
Z ¹² represents -CO- or -CO-CH=CH- and particularly preferably -CO.

R ¹² represents a hydrogen atom, a straight-chain alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, an allyloxy group or a structure represented by formula (1-3), particularly preferably a methyl group Ethyl group, a propyl group, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group or a structure represented by formula (1-3), and more preferably a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenyl group, a acryloylamino group, a methacryloylamino group or a structure represented by formula (1-3).

Specific examples of the compound represented by formula (4) are shown below without limiting this invention.

The compound represented by formula (4) can be prepared without any particular limitation by methods described in, for example JP 2002- 536 529 A or are described in Molecular Crystals and Liquid Crystals (2010), 530, 169-174.

[Compound represented by formula (5)]

(In Formel (5) stellt Z¹³ -CO- oder -CO-CH=CH- dar,
Z¹⁴ stellt -CO- oder -CH=CH-CO- dar,
jedes von R¹³ und R¹⁴ stellt unabhängig voneinander ein Wasserstoffatom, eine geradkettige Alkylgruppe mit 1 bis 4 Kohlenstoffatomen, eine Methoxygruppe, eine Ethoxygruppe, eine Phenylgruppe, eine Acryloylaminogruppe, eine Methacryloylaminogruppe, eine Allyloxygruppe oder eine durch Formel (1-3) dargestellte Struktur dar.)
Z¹³ stellt -CO- oder -CO-CH=CH- und vorzugsweise -CO- dar.The compound used for the liquid crystal composition of this invention is a compound represented by the following formula (5), and preferably a liquid crystal compound represented by the following formula (5) which does not have a (meth)acrylate group.

(In formula (5) Z ¹³ represents -CO- or -CO-CH=CH-,
Z ¹⁴ represents -CO- or -CH=CH-CO-,
each of R ¹³ and R ¹⁴ independently represents a hydrogen atom, a straight-chain alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, an allyloxy group or a structure represented by formula (1-3). depict.)
Z ¹³ represents -CO- or -CO-CH=CH- and preferably -CO-.

Each of R ¹³ and R ¹⁴ independently represents a hydrogen atom, a straight-chain alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, an allyloxy group or a structure represented by formula (1-3). , particularly preferably a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group or a structure represented by formula (1-3), and even more preferably a methyl group, an ethyl group, a methoxy group , an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group or a structure represented by formula (1-3).

Specific examples of the compound represented by formula (5) are shown below without limiting this invention.

[Compound represented by formula (6)]

The compound used for the liquid crystal composition of this invention is a compound represented by the following formula (6), and preferably a polymerizable liquid crystal compound represented by the following formula (6), and has two (meth)acrylate groups.

(In formula (6), each of n2 and n3 independently represents an integer from 3 to 6 and

each of R ¹⁵ and R ¹⁶ independently represents a hydrogen atom or a methyl group.)

In formula (6), each of n2 and n3 independently represents an integer of 3 to 6, and preferably each of n2 and n3 represents 4.

In formula (6), each of R ¹⁵ and R ¹⁶ independently represents a hydrogen atom or a methyl group, and preferably each of R ¹⁵ and R ¹⁶ represents a hydrogen atom.

Specific examples of the compound represented by formula (6) are shown below without limiting this invention.

The polymerizable liquid crystal compound represented by formula (6) can be prepared without particular limitation by a method described in, for example JP 2009- 184 975 A is described.

(Preferred embodiment of the liquid crystal composition of this invention

• (B) Flüssigkristallzusammensetzung enthaltend die durch die Formeln (4), (5) und (6) dargestellten Verbindungen, worin in den Formeln (4) und (5) mindestens zwei von R¹², R¹³ und R¹⁴ denselben Substituenten darstellen und besonders bevorzugt R¹², R¹³ und R¹⁴ denselben Substituenten darstellen,
• (C) Flüssigkristallzusammensetzung enthaltend die durch die Formeln (4), (5) und (6) dargestellten Verbindungen, worin in Formel (4) n1 4 ist,
• (D) Flüssigkristallzusammensetzung enthaltend die durch die Formeln (4), (5) und (6) dargestellten Verbindungen, worin in den Formeln (4) und (6) jedes von R¹¹, R¹⁵ und R¹⁶ ein Wasserstoffatom darstellt,
• (E) Flüssigkristallzusammensetzung enthaltend die durch die Formeln (4), (5), (6) dargestellten Verbindungen, worin in den Formeln (4) und (5) jedes von Z¹², Z¹³ und Z¹⁴ -COdarstellt,
• (F) Flüssigkristallzusammensetzung enthaltend die durch die Formeln (4), (5) und (6) dargestellten Verbindungen, worin in den Formeln (4) und (5) jedes von R¹², R¹³ und R¹⁴ unabhängig voneinander eine geradkettige Alkylgruppe mit 1 bis 4 Kohlenstoffatomen, eine Methoxygruppe, eine Ethoxygruppe oder eine Phenylgruppe darstellt und vorzugsweise jedes von R¹², R¹³ und R¹⁴ unabhängig voneinander eine Methylgruppe, eine Ethylgruppe, eine Methoxygruppe, eine Ethoxygruppe oder eine Phenylgruppe darstellt.

Preferred embodiments of the liquid crystal composition of this invention are as follows.

• (B) Liquid crystal composition containing the compounds represented by formulas (4), (5) and (6), wherein in formulas (4) and (5) at least two of R ¹² , R ¹³ and R ¹⁴ represent the same substituent and especially preferably R ¹² , R ¹³ and R ¹⁴ represent the same substituent,
• (C) Liquid crystal composition containing the compounds represented by formulas (4), (5) and (6), wherein in formula (4) n1 is 4,
• (D) Liquid crystal composition containing the compounds represented by formulas (4), (5) and (6), wherein in formulas (4) and (6), each of R ¹¹ , R ¹⁵ and R ¹⁶ represents a hydrogen atom,
• (E) A liquid crystal composition containing the compounds represented by formulas (4), (5), (6), wherein in formulas (4) and (5), each of Z ¹² , Z ¹³ and Z ¹⁴ represents -CO,
• (F) Liquid crystal composition containing the compounds represented by formulas (4), (5) and (6), wherein in formulas (4) and (5), each of R ¹² , R ¹³ and R ¹⁴ independently has a straight-chain alkyl group 1 to 4 carbon atoms, a methoxy group, an ethoxy group or a phenyl group, and preferably each of R ¹² , R ¹³ and R ¹⁴ independently represents a methyl group, an ethyl group, a methoxy group, an ethoxy group or a phenyl group.

(Composition ratio of polymerizable liquid crystal compound)

The liquid crystal composition of this invention preferably contains, based on the compound represented by formula (6), 3 to 50 mass% of the compound represented by formula (4) and 0.01 to 10 mass% of the compound represented by formula (5) and particularly preferably, again based on the compound represented by formula (6), 5 to 40% by mass of the compound represented by formula (4) and 0.1 to 5% by mass of the compound represented by formula (5). With a composition ratio controlled in these ranges, the liquid crystal composition is further improved in terms of the crystallization suppressing effect.

<Second Embodiment of This Invention>

[Method for producing the liquid crystal composition (not covered by the language of the claims)]

The liquid crystal composition of this invention can typically be obtained by the production method described below. Specifically, a liquid crystal compound represented by the following formula (I) and a liquid crystal compound represented by the following formula (II) can be obtained simultaneously by combining a compound represented by the formula (III) with a carboxylic acid represented by the following formula (IV) and a Carboxylic acid represented by the following formula (V) can be implemented. P ¹ -Sp ¹ -T ¹ -A ²¹ -BA ²² -T ¹ -Sp ¹ -P ¹ Formula (I) P ¹ -Sp ¹ -T ¹ -A ²¹ -B- ^A23 -T ² -X Formula (II) HY ¹ -BY ² H Formula (III) P ¹ -Sp ¹ -T ¹ -COOH Formula (IV) Formula (V) X-T2-COOH

(In formulas (I) to (IV), P ¹ represents a polymerizable group. Sp ¹ represents an optionally substituted divalent aliphatic group with 3 to 12 carbon atoms, in which one CH ₂ group or two or more non-adjacent CH ₂ - Groups in the aliphatic group may be replaced by -O-, -S-, -OCO-, -COO or -OCOO-. T ¹ represents a 1,4-phenylene group. T ² represents a single bond or a divalent group with a cyclic structure. A ²¹ represents -COO-, -CONR ¹ - (R ¹ represents a hydrogen atom or a methyl group), or -COS. Each of A ²² and A ²³ represents -OCO-, -NR ^1A CO- (R ^1A represents a hydrogen atom or a methyl group) or -SCO. B represents an optionally substituted divalent group with a cyclic structure.

X is a hydrogen atom, a branched or straight -chain alkyl group with 1 to 12 carbon atoms, a branched or straight -chain alkoxy group with 1 to 12 carbon atoms, a phenyl group, a cyano group, a halogen atom, a nitr group, an acetyl group or a vinyl group. Each of y ² - and Y ² independently represents O, NR ^1B (R ^1B represents a hydrogen atom or a methyl group) or S.)

X places a hydrogen atom, a branched or straight -chain alkyl group with 1 to 12 carbon atoms, a branched or straight -chain alkoxy group with 1 to 12 carbon atoms, a phenyl group, a cyana group, a halogen atom, a nitr group, an acetyl group or a vinyl group, a formyl group, -OC (=O)R (R represents an alkyl group with 1 to 12 carbon atoms), an N-acetylamide group, an acryloylamino group, an N,N-dimethylamino group, an N-maleimide group, a methacryloylamino group, an allyloxy group, an N-alkyloxycarbamoyl group with the alkyl group thereof having 1 to 4 carbon atoms, an allyloxycarbamoyl group, an N-(2-methacryloyloxyethyl)carbamoyloxy group, an N-(2-acryloyloxyethyl)carbamoyloxy group or a structure represented by the following formula (VI). -A ⁴ -T ⁴ -Sp ² -P ² Formula (VI)

(In formula (VI), P ² represents a polymerizable group or a hydrogen atom, each of A ⁴ , T ⁴ and Sp ² is equivalent to A ²² , T ² and Sp ¹ , respectively. Now, according to this preparation method, it is prepared using two various carboxylic acid species as part of the starting materials, it is possible to prepare a liquid crystal composition excellent in crystallization suppressing effect, solubility and liquid crystallinity in a one-pot method.

According to the production method, by reacting the compound represented by formula (III) with the carboxylic acid represented by formula (IV) and the carboxylic acid represented by formula (V), not only the liquid crystal compound represented by formula (I) and that represented by formula (II). Liquid crystal compound but also the liquid crystal compound represented by formula (II-a) can be obtained simultaneously. XT ² -A ²³ -BA ²³ -T ² -X Formula (II-a)

(In formula (II-a), B represents an optionally substituted divalent group with a cyclic structure. A ²³ is equivalent to A ²³ in formula (II). T ² is equivalent to T ² in formula (II). X is equivalent with X in formula (II).

<Synthesis scheme, synthesis order and reaction conditions>

Now, the expression "simultaneously" obtaining the liquid crystal compound represented by formula (I) and the liquid crystal compound represented by formula (II) means not only that both liquid crystal compounds are synthesized at the same time but also that they are obtained in a one-pot method by The compound represented by formula (III) is reacted with the carboxylic acid represented by formula (IV) and the carboxylic acid represented by formula (V).

An exemplary synthesis scheme for the process for producing a liquid crystal composition of this invention is shown below. For this description, it should be noted that compounds (I) to (V) each represent the compounds represented by formulas (I) to (V).

Synthesis scheme

$$\begin{array}{l}\text{Connection}\left(\text{IV}\right)+\text{Connection}\stackrel{verbindunG\left(III\right)}{\to }\text{Connection}\left(\text{I}\right)+\\ \text{Connection}\left(\text{II}\right)\end{array}$$

$$\begin{array}{l}\text{Connection}\left(\text{IV}\right)+\text{Connection}\stackrel{verbindunG\left(III\right)}{\to }\text{Connection}\left(\text{I}\right)+\\ \text{Connection}\left(\text{II}-\text{a}\right)\end{array}$$

In the method for producing a liquid crystal composition of this invention, the synthesis order is not particularly limited and may follow any other order other than the synthesis scheme shown above.

The order of addition of the carboxylic acid represented by formula (IV) and the carboxylic acid represented by formula (V) is not particularly limited.

It is preferred that the process for producing a liquid crystal composition of this invention includes a step of activating the carboxylic acid represented by formula (IV) and the carboxylic acid represented by formula (V) by converting them into a mixed acid anhydride or acid halide, and that after In the activation step, the compound represented by formula (III) is reacted with the thus activated carboxylic acid represented by formula (IV) or carboxylic acid represented by formula (V) in the presence of a base.

An activator used for the activation step is not particularly limited, typically methanesulfonyl chloride or toluenesulfonyl chloride is used. The base is also not particularly limited, for which a tertiary amine (e.g. triethylamine or diisopropylethylamine) or an inorganic salt is usually used. The activation step preferably takes place with ice cooling.

The compound represented by formula (III) is preferably added after the activation step in view of preventing the activator from adversely affecting the compound represented by formula (III). The compound represented by formula (III) is preferably added after the activation step and in the presence of a base to the activated carboxylic acid represented by formula (IV) and carboxylic acid represented by formula (V) under ice cooling. While there is no particular limitation on the condition under which the compound represented by formula (III) is added to the activated carboxylic acid represented by formula (IV) and carboxylic acid represented by formula (V), the condition is preferably 0 to 30° C and particularly preferably 10 to 25°C.

<Compound represented by formula (III)>

In the process for producing a liquid crystal composition of this invention, the compound represented by the following formula (III) can be used as part of the starting material. HY ¹ -BY ² H Formula (III)

(In formula (III), B represents an optionally substituted divalent group having a cyclic structure. Each of Y ² and Y ² independently represents O, NR ^1C (R ^1C represents a hydrogen atom or a methyl group), or S.)

B represents an optionally substituted divalent group having a cyclic structure and is preferably a linking group included in the group of the following linking groups (VI).

In the group of formulas (VI), each of R ²⁰ to R ²⁸ independently represents a hydrogen atom, a branched or straight chain alkyl group having 1 to 4 carbon atoms, a branched or straight chain alkoxy group having 1 to 4 carbon atoms, a halogen atom or an alkoxycarbonyl group having 1 up to 3 carbon atoms.

Each of R ²⁰ to R ²⁸ independently represents a hydrogen atom, a branched or straight chain alkyl group having 1 to 4 carbon atoms, and particularly a hydrogen atom or a straight chain alkyl group having 1 or 2 carbon atoms.

Jedes von Y¹ und Y² stellt unabhängig voneinander O, NR^1D (R^1D stellt ein Wasserstoffatom oder eine Methylgruppe dar) oder S und vorzugsweise O dar. It is particularly preferred that B is a linking group included in the following group of linking groups (VIII).

Each of Y ¹ and Y ² independently represents O, NR ^1D (R ^1D represents a hydrogen atom or a methyl group), or S and preferably O.

Examples of the compounds represented by formula (III) are shown below without limiting this invention.

<Carboxylic acid represented by formula (IV)>

In the process for producing a liquid crystal composition of this invention, the carboxylic acid represented by the following formula (IV) can be used as part of the starting material. P ¹ -Sp ¹ -T ¹ -COOH Formula (IV)

In formula (IV), P ¹ represents a polymerizable group. Sp ¹ represents an optionally substituted divalent aliphatic group having 3 to 12 carbon atoms, wherein one CH ₂ group or two or more non-adjacent CH ₂ groups in the aliphatic group -O-, -S-, -OCO-, -COO- or -OCOO- can be substituted. T ¹ represents a 1,4-phenylene group.

P ¹ represents a polymerizable group without any particular limitation. For details and preferred selections of the polymerizable group, reference can be made to paragraphs [0161] to [0171] of JP 2002- 129 162 A Reference is made, the content of which can be incorporated into this description. P ¹ preferably represents an ethylenically unsaturated double bond group, particularly preferably a methacryloyl group or acryloyl group and in particular an acryloyl group.

Sp ¹ represents an optionally substituted divalent aliphatic group having 3 to 12 carbon atoms, in which one CH ₂ group or two or more non-adjacent CH ₂ groups in the aliphatic group are replaced by -O-, -S-, -OCO-, - COO- or -OCOO- can be replaced.

Sp ¹ represents an optionally substituted divalent alkylene group with 3 to 12 carbon atoms, particularly preferably an alkylene group with 3 to 8 carbon atoms and even more preferably an alkylene group with 3 to 6 carbon atoms, the non-adjacent methylene groups in the alkylene group being substituted by -O- can. While the alkylene group may be branched or unbranched, it is preferably a straight chain alkylene group with no branching.

Examples of the carboxylic acid represented by formula (IV) are shown below without limiting this invention.

<Carboxylic acid represented by formula (V)>

In the process for producing a liquid crystal composition of this invention, the carboxylic acid represented by the following formula (V) can be used as part of the raw material. XT ² -COOH Formula (V)

In formula (V), T ² represents a single bond or a divalent group having a cyclic structure. a cyano group, a halogen atom, a nitro group, an acetyl group, a vinyl group, a formyl group, -OC(=O)R (R represents an alkyl group with 1 to 12 carbon atoms), an N-acetylamide group, an acryloylamino group, an N,N -Dimethylamino group, an N-maleimide group, a methacryloylamino group, an allyloxy group, an N-alkyloxycarbamoyl group with the alkyl group thereof having 1 to 4 carbon atoms, an allyloxycarbamoyl group, an N-(2-methacryloyloxyethyl)carbamoyloxy group, an N-(2-acryloyloxyethyl)carbamoyloxy group or a structure represented by the formula (VI).

T ² represents a single bond or a divalent group with a cyclic structure, preferably a single bond or a divalent group with a divalent aromatic hydrocarbon group or divalent heterocyclic group, and particularly preferably a divalent aromatic hydrocarbon group or divalent heterocyclic group.

The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 22, more preferably 6 to 14, even more preferably 6 to 10 and further preferably 6. If it has six carbon atoms, the divalent aromatic hydrocarbon group preferably has bonds at the meta position or para position and in particular bonds at the para position.

The divalent heterocyclic group preferably has a five-membered, six-membered or seven-membered heterocycle. The five-membered ring or the six-membered ring is particularly preferred and the six-membered ring is most preferred. The heteroatom constituting the heterocycle is preferably a nitrogen atom, oxygen atom or sulfur atom. The heterocycle is preferably an aromatic heterocycle. The aromatic heterocycle is generally an unsaturated heterocycle. The unsaturated heterocycle preferably has the largest possible number of double bonds. Examples of the heterocycle include a furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiine ring, pyridine ring, piperidine ring, Oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring.

The divalent aromatic hydrocarbon group or the divalent heterocyclic group may have an additional divalent linking group. The divalent linking group is preferably an alkenyl group having 2 to 4 carbon atoms, and most preferably an alkenyl group having 2 carbon atoms.

In the process for producing a liquid crystal composition of this invention, T ² is preferably a linking group included in the following group of linking groups (VII).

X places a hydrogen atom, a branched or straight -chain alkyl group with 1 to 12 carbon atoms, a branched or straight -chain alkoxy group with 1 to 12 carbon atoms, a phenyl group, a cyana group, a halogen atom, a nitr group, an acetyl group or a vinyl group, preferably a hydrogen atom, one branched or straight chain alkyl group with 1 to 4 carbon atoms, a straight chain alkoxy group with 1 or 2 carbon atoms or a phenyl group, even more represents a branched or straight chain alkyl group with 1 to 4 carbon atoms, a straight chain alkoxy group with 1 or 2 carbon atoms or a phenyl group and in particular a straight chain alkyl group with 1 to 4 carbon atoms or a phenyl group.

X preferably represents an acryloylamino group, a methacryloylamino group, an allyloxy group, an N-alkyloxycarbamoyl group with the alkyl group thereof having 1 to 4 carbon atoms, an allyloxycarbamoyl group or a structure represented by the formula (V-I), and particularly preferably an acryloylamino group, a methacryloylamino group or a structure represented by Structure shown in formula (V-I).

In formula (VI), P ² represents a polymerizable group or a hydrogen atom, with the polymerizable group being preferred. The preferred choice for the polymerizable group is equivalent to that previously described for P ¹ . Also A ⁴ , T ⁴ and Sp ² are independently equivalent to A ²³ , T ² and Sp ¹ which are defined by the same preferred selections. It is particularly preferred that in formula (VI) P ² represents a methacryloyl group or an acryloyl group, Sp ² represents a divalent unbranched alkylene group having 1 to 12 carbon atoms, where one CH ₂ group or two or more non-adjacent CH ₂ groups in the alkylene group can be replaced by -O-, -OCO-, -COO- or -OCOO-, T ⁴ represents a 1,4-phenylene group and A ⁴ represents -OCO-.

Examples of the carboxylic acid represented by formula (V) are shown below without limiting this invention.

In the method for producing a liquid crystal composition of this invention, the feed molar ratio of the carboxylic acid represented by formula (IV) to the carboxylic acid represented by formula (V) is preferably in the range of 75:25 to 99:1, particularly preferably in the range of 77:33 to 95:5 and particularly preferably in the range from 80:20 to 90:10.

<Liquid crystal compound represented by formula (I) and liquid crystal compound represented by formula (II)>

In the process for producing a liquid crystal composition of this invention, the liquid crystal compound represented by the following formula (I) and the liquid crystal compound represented by the following formula (II) are simultaneously obtained. P ¹ -Sp ¹ -T ¹ -A ²¹ -BA ²² -T ¹ -Sp ¹ -P ¹ Formula (I) P ¹ -Sp ¹ -T ¹ -A ²¹ -BA ²³ -T ² -X Formula (II)

In formulas (I) and (II), P ¹ represents a polymerizable group. Sp ¹ represents an optionally substituted divalent aliphatic group having 3 to 12 carbon atoms, where one CH ₂ group or two or more non-adjacent CH ₂ groups in the aliphatic group can be replaced by -O-, -S-, -OCO-, -COO- or -OCOO-. T ¹ represents a 1,4-phenylene group. T ² represents a single bond or a divalent group with a cyclic structure. A ²¹ represents -COO-, -CONR ^1E - (R ^1E represents a hydrogen atom or a methyl group) or - COS-. Each of A ²² and A ²³ independently represents -OCO-, NR ^1F CO- (R ^1F represents a hydrogen atom or a methyl group), or -SCO-. B represents an optionally substituted divalent group having a cyclic structure represents. -OC(=O)R (R represents an alkyl group with 1 to 12 carbon atoms), an N-acetylamide group, an acryloylamino group, an N,N-dimethylamino group, an N-maleimide group, a methacryloylamino group, an allyloxy group, an N-alkyloxycarbamoyl group with the alkyl group thereof having 1 to 4 carbon atoms, an allyloxycarbamoyl group, an N-(2-methacryloyloxyethyl)carbamoyloxy group, an N-(2-acryloyloxyethyl)carbamoyloxy group or a structure represented by the formula (VI).

Preferred selections for P ¹ , Sp ¹ , T ² , B and X in formulas (I) and (II) are the same as the preferred selections for P ¹ , Sp ¹ , T ² , B and X in formulas (III) to (V).

In formulas (I) and (II), A ²¹ represents -COO-, -CONR ^1E - (R ^1E represents a hydrogen atom or a methyl group) or -COS- and preferably -COO-.

In formulas (I) and (II), each of A ²² and A ²³ independently represents -OCO-, -NR ^1F CO- (R ^1F represents a hydrogen atom or a methyl group) or -SCO- and preferably -OCO- .

In formulas (I) and (II), it is particularly preferred that A ²¹ represents -COO- and that each of A ²² and A ²³ represents -OCO.

Specific examples of the compound represented by formula (I) other than those 1-1 to 1-14 described above are shown below without limiting this invention.

Specific examples of the compound represented by formula (II) are shown below without limiting this invention.

<Chemical composition of liquid crystal composition>

In the process for producing a liquid crystal composition of this invention, the production molar ratio of the compound represented by formula (I) to the compound represented by formula (II) is preferably in the range of 50:50 to 98:2, particularly preferably in the range of 60: 40 to 96:4 and particularly preferably in the range from 70:30 to 94:6.

In the process for producing a liquid crystal composition of this invention, the production molar ratio of the compound represented by formula (I) to the compound represented by formula (II) and the compound represented by formula (II-a) is preferably in the range of 50:40 :10 to 94.99:5:0.01 and particularly preferably in the range from 60:30:10 to 94.9:8:0.1.

The composition mass ratio of the compound represented by formula (I) to the compound represented by formula (II) in the liquid crystal composition prepared by the method ren for preparing a liquid crystal composition of this invention is preferably in the range of 50:50 to 95:5, more preferably in the range of 60:40 to 95:5 and particularly preferably in the range of 70:30 to 92:8.

As for the composition mass ratios among the compound represented by formula (I), the compound represented by formula (II) and the compound represented by formula (II-a) in the liquid crystal composition obtained by the method for producing a liquid crystal composition, particularly When using an optical compensation film, it is preferred that 3 to 50% by mass of the compounds represented by formula (II), 0.01 to 10% by mass of the compound represented by formula (II-a), based on Compound represented by formula (I) is contained therein, and it is particularly preferred that 5 to 40% by mass of the compounds represented by formula (I) is based on 0.1 to 5% by mass of the compound represented by formula (II). to the compound represented by formula (II-a), are contained therein.

As for the composition mass ratios among the compound represented by formula (I), the compound represented by formula (II) and the compound represented by formula (II-a) in the liquid crystal composition obtained by the method for producing a liquid crystal composition of the present invention, particularly when used in a reflection film, it is preferred that 3 to 50 mass% of the compound represented by formula (II) and 0.01 to 10 mass% of the compound represented by formula (II-a) based on The compound represented by formula (I) is contained therein, and it is particularly preferred that 5 to 40% by mass of the compound represented by formula (I) is 0.1 to 5% by mass of the compound represented by formula (II), based on the compound represented by formula (II-a) is contained therein.

[Polymer material, film configuration]

The polymer material and the film of the present invention each have the polymerizable liquid crystal compound or the optically anisotropic layer obtained by fixing the orientation (for example, homogeneous orientation, homeotropic orientation, cholesteric orientation, hybrid orientation, etc.) of the liquid crystal composition of the present invention and has optical anisotropy . The optically anisotropic layer can have two or more optically isotropic layers. The film is used as an optical compensation film, 1/2 wavelength film, 1/4 wavelength film or phase difference film of liquid crystal display devices based on TN mode, IPS mode, etc. and as a reflection film utilizing the selective reflection attributable to cholesteric alignment, usable. Particularly preferably, the film according to the invention is a film in which the optically anisotropic layer is obtainable by fixing a cholesteric orientation of the liquid crystal compounds, and a film which is obtainable by fixing a cholesteric orientation of the polymerizable liquid crystal compound according to the invention or the liquid crystal compounds of the liquid crystal composition according to the invention.

Therefore, it is preferred that the liquid crystal composition of the present invention contains various additives depending on the application. The additives are described below.

(Other additives)

The liquid crystal composition of the present invention, for example, when used as a reflection film utilizing the selective reflection attributable to the cholesteric orientation, may contain not only the polymerizable liquid crystal but also optionally a solvent, a compound having a chiral carbon atom, a polymerization initiator (which will be described later) and other additives ( e.g. a cellulose ester).

Optically active compound (chiral agent):

The liquid crystal composition may have a cholesteric liquid crystal phase and for this purpose preferably contains an optically active compound. Note that when the rod-like liquid crystal compound has a chiral carbon atom, it is sometimes possible to form the cholesteric liquid crystal phase in a stable manner without adding an optically active compound. The optically active compound is composed of notoriously known various chiral agents (e.g. those described in “Ekisho Debaisu Handobukku (Handbook of Liquid Crystal Devices)”, Chapter 3, Section 4-3, “TN, STN-yo Kairaru-zai (Chiral Agent for TN and STN)", p. 199, published by 142th Committee of Japan Society for Promoting Science, 1989) can be selected. While the optically active compound generally has a chiral carbon atom, a compound with axial chirality or a compound with planar chirality that does not have a chiral carbon atom can also be used as the chiral agent. Examples of the axial chirality compound and the planar chirality compound include binaphthyl, helicene, paracyclophane and derivatives thereof. The optically active compound (chiral agent) may have a polymerizable group. When the optically active compound has a polymerizable group and the rod-like liquid crystal compound used in combination also has a polymerizable group, it is possible to produce a polymer having a repeating unit derived from the rod-like liquid crystal compound and a repeating unit derived from the optically active compound by means of a polymerization reaction between the polymerizable optically active compound and the polymerizable rod-like liquid crystal compound. In this embodiment, the polymerizable group of the polymerizable optically active compound is preferably the same species as the polymerizable group of the polymerizable rod-like liquid crystal compound. Accordingly, the polymerizable group of the optically active compound is also preferably an unsaturated polymerizable group, an epoxy group or aziridinyl group, particularly preferably an unsaturated polymerizable group and in particular an ethylenically unsaturated polymerizable group.

The optically active compound can also be a liquid crystal compound.

The consumption amount of the optically active compound in the liquid crystal composition is preferably 1 to 30 mol% of the liquid crystal compound used in combination. The lower the amount of optically active compound used, the better, since liquid crystallinity is less likely to be adversely affected. Accordingly, the optically active compound used as a chiral agent preferably has a high twisting capacity, so that a twisted alignment with a desired helical pitch is obtained with a small consumption amount. Such a chiral agent, which shows a high twisting capacity, is, for example, by the in JP 2003-287 623 A described by way of example, which are preferably applicable to the present invention.

Polymerization initiator

The polymerization initiator includes a thermal polymerization initiator and a photopolymerization initiator, and it is preferred to use a photopolymerization initiator.

Examples of the photopolymerization initiator include α-carbonyl compounds (described in the descriptions of US 2,367,661 A and US 2,367,670 A ), acyloin ether (described in the description of US 2,448,828 A ) α-hydrocarbon-substituted aromatic acyloin compounds (described in the description of US 2,722,512 A ), polynuclear quinone compounds (described in the descriptions of US 3,046,127 A and US 2,951,758 A ), a combination of a triarylimidazole dimer and p-aminophenyl ketone (described in the description of US 3,549,367 A ), acridine and phenazine compounds (described in the description of JP S60- 105 667 A and US 4,239,850 A ), an oxadiazole compound (described in the description of US 4,212,970 A ) and acylphosphine oxide compounds (described in JP S63- 40 799 B2 , JP H05-29 234 B2 , JP H10-95 788 A and JP H10-29 997 A ) a.

The consumption amount of photopolymerization initiator is preferably 0.01 to 20% by mass of the solids content of the coating liquid and particularly preferably 0.5 to 5% by mass.

(Solvent)

Preferably, an organic solvent is used to dissolve the liquid crystal composition. Examples of the organic solvent include amides (e.g. N,N-dimethylformamide), sulfoxides (e.g. dimethyl sulfoxide), heterocyclic compounds (e.g. pyridine), hydrocarbons (e.g. benzene and hexane), alkyl halides (e.g. chloroform and dichloromethane), esters (e.g. methyl acetate and butyl acetate), ketones (e.g. acetone, methyl ethyl ketone, cyclohexanone) and ethers (e.g. tetrahydrofuran and 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents can be used in combination.

When the liquid crystal composition of the present invention is used for an optical compensation film of a liquid crystal display device, the liquid crystal composition may contain a An orientation control agent, a surfactant, a fluorine-containing polymer, etc. are included in addition to the polymerization initiator and the above-mentioned solvent.

(Means for controlling orientation)

The alignment control agent in this invention refers to a compound which is usually added to a coating liquid of the liquid crystal composition of the present invention and, after coating, segregates to the surface of the liquid crystal composition, i.e. to the air interface, so that it is capable of controlling the alignment of the liquid crystal composition at the air interface (alignment means for the air interface). Alternatively, this means a compound which, after coating, segregates at the interface between the layer of the liquid crystal composition and the substrate and controls the alignment of the liquid crystal composition on the substrate side and is exemplified by an onium salt.

As an alignment control agent at the air interface, a low molecular alignment control agent or a polymeric alignment control agent can be commonly used. For the low molecular alignment control agent, reference can be made to the descriptions, for example, paragraphs [0009] to [0083] of JP 2002- 20 363 A , paragraphs [0111] to [0120] of JP 2006- 106 662 A and paragraphs [0021] to [0029] of JP 2012- 211 306 A Reference is made to the contents of which are included in this description. For the polymeric alignment control agent, reference may be made to the descriptions, for example, in paragraphs [0021] to [0057] of JP 2004- 198 511 A and paragraphs [0121] to [0167] of JP 2006- 106 662 A Reference is made to the contents of which are included in this description.

The consumption amount of the alignment control agent is preferably 0.01 to 10 mass% relative to the solid content in the coating liquid of the liquid crystal composition according to the invention, and more preferably 0.05 to 5 mass%.

By using such an alignment control agent and an alignment film, the liquid crystal compound of the present invention can be maintained in a homogeneous alignment in which molecules are aligned parallel to the surface of the layer.

When the onium salt or the like is used as an alignment control agent, it becomes possible to promote the homeotropic alignment of the liquid crystal compounds at the interface. Regarding the onium salt acting as a vertical alignment agent, reference can be made to paragraphs [0052] to [0108] of JP 2006- 106 662 A Reference is made, the content of which is incorporated into this description.

The consumption amount of the onium salt is preferably 0.01 to 10% by mass of the solid content in the coating liquid containing the liquid crystal composition of the present invention, and particularly preferably 0.5 to 5% by mass.

(surfactant)

The surfactant is represented by notoriously known compounds and in particular by fluorine-containing compounds. As far as the surfactant is concerned, reference can be made, for example, to those in paragraphs [0028] to [0056] of JP 2001-330 725 A and to those in paragraphs [0199] to [0207] of JP 2006-106 662 A Reference is made, the contents of which are included in this description.

The consumption amount of surfactant is preferably 0.01 to 10% by mass of the solids content in the coating liquid containing the liquid crystal composition according to the invention, and particularly preferably 0.5 to 5% by mass.

(Other additives applicable to optical compensation film)

As for other additives applicable to an optical compensation film, reference can be made, for example, to those described in paragraphs [0099] to [0101] of JP 2005-97 377 A Reference is made, the content of which is incorporated into the present description.

The film of the invention can be formed, for example, by coating the liquid crystal composition of the invention. A preferred method for forming the film of the invention is such that a composition containing at least the liquid crystal composition of the invention is coated on the surface of a support or on the surface of the alignment film formed thereon, the liquid crystal composition is aligned into a desired state, it is polymerized is cured and the alignment state of the liquid crystal composition is fixed.

The liquid crystal composition can be applied by any well-known method (e.g., extrusion coating, direct gravure coating, reverse gravure coating, die coating, bar coating and spin coating). The liquid crystalline molecules are preferably fixed while maintaining them in the aligned state. The fixation is preferably carried out by a polymerization reaction involving the polymerizable group introduced into the liquid crystalline molecules.

The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. The photopolymerization reaction is preferred.

Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Patent Nos. 2,367,661 and ibid. 2,367,670 ), acyloin ether (described in US Patent No. 2,448,828 ), α-hydrocarbon-substituted aromatic acyloin compounds (described in U.S. Patent No. 2,722,512 ), polynuclear quinone compounds (described in US Patent Nos. 3,046,127 and ibid. 2,951,758 ), a combination of a triarylimidazole dimer and p-aminophenyl ketone (described in US Patent No. 3,549,367 ), acridine and phenazine compounds (described in JP S60- 105 667 A and US Patent No. 4,239,850 ), an oxadiazole compound (described in US Patent No. 4,212,970 ) and acylphosphine oxide compounds (described in JP S63- 40 799 B2 , JP H05-29 234 B2 , JP H10-95 788 A and JP H10-29 997 A ) a.

The consumption amount of photopolymerization initiator is preferably 0.01 to 20% by mass of the solids content of the coating liquid and particularly preferably 0.5 to 5% by mass. Ultraviolet radiation is preferably used for the light irradiation for polymerizing discotic liquid crystalline compounds. The irradiation dose is preferably 20 mJ/cm ² to 50 J/cm ² and particularly preferably 100 to 800 mJ/cm ² . The light irradiation can be carried out with heating so that the photopolymerization reaction is accelerated.

The thickness of the optically anisotropic layer composed of the liquid crystal composition is preferably 0.1 to 50 µm, and more preferably 0.5 to 30 µm.

For the particular case in which the selective reflectivity of the film is used with the cholesteric orientation of the liquid crystal compounds fixed therein, the thickness is preferably 1 to 30 µm and most preferably 2 to 20 µm. The total coating amount of the compound represented by formula (4) and the compound represented by formula (6) in the liquid crystal layer (coating amount of the liquid crystal alignment accelerators) is preferably 0.1 to 500 mg/m ² , particularly preferably 0.5 to 450 mg/m ² , further preferably 0.75 to 400 mg/m ² and most preferably 1.0 to 350 mg/m ² .

On the other hand, when the optically anisotropic layer is used as an optical compensation film (e.g. A plate with a state of homogeneous alignment fixed therein and C plate with a state of homeotropic alignment fixed therein), its thickness is preferably 0.1 to 50 μm and particularly preferably 0.5 to 30 µm.

The alignment film can be formed by a technique such as rubbing the organic compound (preferably polymer), oblique evaporation of an inorganic compound, forming a layer with microgrooves, or accumulation of an organic compound by the Langmuir-Blodgett method (LB film) (e.g. ω-tricosanoic acid, Dioctadecylmethyl ammonium chloride, methyl stearate). Also known is an alignment film which exhibits the alignment function after being exposed to an electric field, a magnetic field or light irradiation. The alignment film formed by rubbing a polymer is particularly preferred. The rubbing process is performed by unidirectionally rubbing the surface of a polymer layer several times with a paper or cloth. The species of polymer used for the alignment film is determined depending on the alignment of the liquid crystal nen molecules (especially the average tilt angle). A polymer, general polymer for forming the alignment film, which is unlikely to reduce the surface energy of the alignment film, is used for the purpose of horizontal alignment of the liquid crystalline molecules (with an average tilt angle of 0 to 50°). A polymer suitable for reducing the surface energy of the alignment film is used for the purpose of vertically aligning the liquid crystalline molecules (with an average tilt angle of 50 to 90°). In order to reduce the surface energy of the alignment film, it is preferred to introduce a C _10-100 hydrocarbon group into a side chain of the polymer.

The species of the polymer are particularly described in literatures concerning optical compensation films using the liquid crystalline molecules adapted to different types of display modes.

The thickness of the alignment film is preferably 0.01 to 5 µm, and more preferably 0.05 to 1 µm. It is also possible to align the liquid crystal molecules for the optically anisotropic layer using the alignment film and then transfer the liquid crystal layer to a transparent support. The liquid crystalline molecules fixed in the aligned state can maintain such an aligned state without an alignment film. If the average tilt angle is less than 5°, rubbing is no longer required and the alignment film is no longer required. However, for the purpose of improving the adhesion between the liquid crystalline molecules and the transparent support, it is also recommended to use an alignment film (described in JP H09- 152 509 A ), which can form a chemical bond between the liquid crystalline molecule and the interface. When the alignment film is used for the purpose of improving adhesion, rubbing can be omitted. When two types of liquid crystal layers are provided on the same side of the transparent support, the liquid crystal layer formed on the transparent support can serve as an alignment film for the liquid crystal layer formed thereon.

The film according to the invention or an optically anisotropic element with the film according to the invention can have the transparent support. A glass plate or a polymer film can be used as the transparent support, with the polymer film being preferably used. When it is stated that “the support is transparent”, it means that the light transmission is 80% or higher. The generally used transparent support is an optically isotropic polymer film. The optical isotropy is preferably represented by an in-plane retardation (Re) of less than 10 nm and preferably less than 5 nm. As far as the optically isotropic transparent support is concerned, the retardation in the thickness direction (Rth) is also preferably less than 10 nm and particularly preferably less than 5 nm.

(Selective reflection property)

The film according to the invention with the cholesteric liquid crystal phase fixed therein from the liquid crystal composition according to the invention preferably shows a selective reflection property, particularly preferably a selective reflection property in the infrared wavelength range. The light reflecting layer with the cholesteric liquid crystal phase fixed therein is described in detail with reference to in JP 2011- 107 178 A and JP 2011- 018 037 A described methods, which are also preferably used in the present invention.

(laminate)

The film according to the invention can preferably also be configured as a laminate made up of a plurality of layers, each of which has the cholesteric liquid crystal phase from the liquid crystal composition according to the invention fixed therein. The liquid crystal composition according to the invention is also suitable for lamination and can therefore easily form such a laminate.

(Optical compensation film)

The film according to the invention can also be used as an optical compensation film.

When the film of the present invention is used as an optical compensation film, the optical properties of the optically anisotropic layer in the optical compensation film are determined based on the optical properties of the liquid crystal cell and in particular based on the change of the display mode. Using the liquid crystal composition according to the invention, it is now possible to produce the optically anisotropic layer with different optical properties that can be adapted to different display modes of the liquid crystal cell.

For example, regarding the optically anisotropic layer for a TN mode liquid crystal cell, reference can be made to the descriptions in JP H06- 214 116 A , US 5,583,679 A , US 5,646,703 A and DE 39 11 620 A1 Reference is made, the contents of which are included in this description. As for the optically anisotropic layer for a liquid crystal cell in IPS mode or FLC mode, reference can be made to the descriptions in JP H09- 292 522 A and JP H10-54 982 A Reference is made, the contents of which are included in this description. As to the optically anisotropic layer for an OCB mode or HAN mode liquid crystal cell, reference may be made to the descriptions in U.S. Patent No. 5,805,253 and the international patent application WO 96/37 804 A1 Reference is made, the contents of which are included in this description. As for the optically anisotropic layer for a liquid crystal cell in STN mode, reference can be made to the description in JP H09- 26 572 A Reference is made, the content of which is included in the present description. As for the optically anisotropic layer for a VA mode liquid crystal cell, reference can be made to the description in Japanese Patent JP 28 66 372 B2 Reference is made, the contents of which are included in the present description.

In the present invention, the film according to the invention is particularly preferably used as an optically anisotropic layer of a liquid crystal cell in IPS mode.

A film having an optically isotropic layer in which the liquid crystal compounds according to the invention are present in a state of homogeneous alignment can be used, for example, as an A-plate. The A plate now refers to a uniaxial birefringent layer, which is characterized in that the refractive index in the slow axis direction is greater than the refractive index in the thickness direction. If the film according to the invention is an A-plate, only a single optically anisotropic layer is sufficient for compensation, provided the layer has an in-plane retardation (Re) of 200 nm to 350 nm at 550 nm.

A film having an optically anisotropic layer in which the liquid crystal compounds of the present invention are in the state of homeotropic alignment is usable as a positive C plate, possibly in combination with a biaxial film or the like. The positive C plate now refers to a uniaxial birefringent layer, which is characterized in that the refractive index in the thickness direction is greater than the refractive index in the plane. The film according to the invention used as a positive C plate preferably has an in-plane retardation (Re) at 550 nm from -10 nm to 10 nm and a thickness-direction retardation (Rth) at 550 nm from -250 to -50 nm, although this depends on the optical properties of the biaxial film to be combined.

[polarization plate]

The present invention also relates to a polarizing plate having at least the film with the optically anisotropic layer (optical compensation film) and a polarizing film. In the polarizing plate having a polarizing film and a protective film attached to at least one side thereof, the optically anisotropic layer is usable as such a protective film.

Alternatively, in a polarizing plate configured to have protective films on both sides of the polarizing film, the optically anisotropic layer is also usable as one of these protective films.

The polarizing film includes an iodine-containing polarizing film, a dye-containing polarizing film using a dichroic dye, and a polyene-based polarizing film. The iodine-containing polarizing film and the dye-containing polarizing film can generally be manufactured using a vinyl alcohol-based film.

The thinner the polarizing film, the thinner the polarizing plate and the liquid crystal display device in which it is incorporated, although the thickness of the polarizing film is not particularly limited. In this regard, the thickness of the polarizing film is preferably 10 µm or less. Since the optical path length in the polarizing film is necessarily longer than the wavelength of light, the minimum thickness of the polarizing film is preferably 0.7 µm or larger, substantially 1 µm or larger, and generally 3 µm or larger.

[Liquid Crystal Display Device]

The present invention also relates to a liquid crystal display device having such a polarizing plate. The liquid crystal display device may have any alignment mode such as TN mode, IPS mode, FLC mode, OCB mode, HAN mode or VA mode without particular limitation. As for the liquid crystal display device using the VA mode, reference can be made to the description in paragraphs [0109] to [0129] of JP 2005- 128 503 A Reference is made, the content of which is included in the present description. As for the liquid crystal display device using the IPS mode, reference can be made to the description in paragraphs [0027] to [0050] of JP 2006- 106 662 A Reference is made, the content of which is included in the present description.

For the liquid crystal display device according to the invention, for example, the A plate and C plate described above can be used.

The optically anisotropic layer can be incorporated into the liquid crystal display device in the form of the polarizing plate obtained by bonding to the polarizing film. Alternatively, the optically anisotropic layer may be incorporated as a viewing angle compensation film selected by the optically anisotropic layer or configured by a laminate combined with another phase difference layer. The other phase difference layer to be combined is selectable depending on the alignment mode of the liquid crystal cell, which requires compensation of the viewing angle.

The optically anisotropic layer may be disposed between the liquid crystal cell and the polarizing film on the viewer side or between the liquid crystal cell and the polarizing film on the backlight side.

In this description, Re(Λ) and Rth(Λ) are the retardation (nm) in the plane and the retardation (nm) along the thickness direction at a wavelength Λ, respectively. Re(Λ) is measured by applying light with a wavelength of Λ nm to a film in the normal direction of the film using KOBRA 21ADH or WR (from Oji Scientific Instruments). The selection of the measurement wavelength is carried out by manually replacing the wavelength-selective filter or by replacing the measured value through the program.

When a film to be analyzed is expressed by a monoaxial or biaxial index ellipsoid, Rth(A) of the film is calculated as follows.

Rth(Λ) is measured using KOBRA 21ADH or WR based on six Re(Λ) values measured for incident light with a wavelength Λ nm in six directions, which are rotated in 100 steps from 0° to 50° relative the normal direction of the sample film using an in-plane slow axis determined by KOBRA 21ADH as a tilt axis (axis of rotation defined in any in-plane direction if the film does not have an in-plane slow axis), a value a hypothetical mean refractive index and a value entered as the thickness value of the film.

Above, if the film to be analyzed has a direction in which the retardation value is zero at a certain inclination angle around the slow axis in the plane starting from the normal direction as the axis of rotation, then the retardation value changes at an inclination angle greater than the inclination angle at a retardation of zero to a negative value, and then Rth(A) of the film is calculated by KOBRA 21ADH or WR.

$$\text{Rth}=\left\{\left(\text{nx}+\text{ny}\right)/2-\text{nz}\right\}\times \text{d}$$

Around the slow axis as the tilt angle (angle of rotation) of the film (if the film does not have a slow axis, then its axis of rotation can be in any direction in the plane of the film), the retardation values are measured in any desired two tilted directions, and based on the data, the estimated value of the average refractive index and the input film thickness value, Rth can be measured according to formulas (1) and (2):
[Mathematical formula] $$\text{re}\left(\theta \right)=\left[nx-\frac{ny\times n\mathrm{e.g}}{\sqrt{\left\{ny\text{sin}\left({\text{sin}}^{-1}\left(\frac{\text{sin}\left(-\theta \right)}{nx}\right)\right)\right\}+{\left\{n\mathrm{e.g}\text{cos}\left({\text{sin}}^{-1}\left(\frac{\text{sin}\left(-\theta \right)}{nx}\right)\right)\right\}}^2}}\right]\times \frac{d}{\text{cos}\left\{{\text{sin}}^{-1}\left(\frac{\text{sin}\left(-\theta \right)}{nx}\right)\right\}}$$

$$\text{Rth}=\left\{\left(\text{nx}+\text{ny}\right)/2-\text{n/a}\right\}\times \text{d}$$

Re (θ) represents a retardation value in the direction inclined by an angle θ from the normal direction; nx represents a refractive index in the plane in the direction of the slow axis; ny represents a refractive index in the plane perpendicular to nx and nz represents a refractive index in the direction perpendicular to nx and ny. And “d” is a thickness of the film.

• Re(A)des Films wird um die langsame Achse herum (definiert durch KOBRA 21ADH oder WR) als Neigungswinkel in der Ebene (Rotationsachse) relativ zu der Normalenrichtung des Films von -50° bis zu +50° bei Intervallen von 10° an insgesamt 11 Punkten mit einem Licht mit einer Wellenlänge von Λ nm, das in der geneigten Richtung appliziert wird, gemessen; und auf Basis der so gemessenen Retardationswerte, des geschätzten Werts des mittleren Brechungsindex und des eingegebenen Filmdickenwerts kann Rth(A)des Films durch KOBRA 21ADH oder WR berechnet werden.

If the film to be analyzed is not expressed by a monoaxial or biaxial index ellipsoid, or that is, if the film does not have an optical axis, then Rth(A) of the film can be calculated as follows:

• Re(A) of the film is measured around the slow axis (defined by KOBRA 21ADH or WR) as the in-plane tilt angle (axis of rotation) relative to the normal direction of the film from -50° up to +50° at intervals of 10° overall 11 points measured with a light with a wavelength of Λ nm applied in the inclined direction; and based on the retardation values thus measured, the estimated value of the average refractive index and the input film thickness value, Rth(A) of the film can be calculated by KOBRA 21ADH or WR.

• Celluloseacylat (1,48), Cycloolefinpolymer (1,52), Polycarbonat (1,59), Polymethylmethacrylat (1,49) und Polystyrol (1,59). KOBRA 21ADH oder WR berechnet nach Eingabe der hypothetischen Werte dieser mittleren Brechungsindizes und der Filmdicke nx, ny und nz. Auf Basis der so berechneten nx, ny und nz wird ferner Nz=(nx-nz)/(nx-ny) berechnet.

In the measurement described above, the hypothetical value of the average refractive index is available from values listed in lists of various optical films in Polymer Handbook (John Wiley & Sons, Inc.). Those that have an unknown mean refractive index can be measured using an Abbe refractometer. The average refractive indices of some major optical films are listed below:

• Cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49) and polystyrene (1.59). KOBRA 21ADH or WR calculates after entering the hypothetical values of these mean refractive indices and the film thickness nx, ny and nz. Based on the nx, ny and nz calculated in this way, Nz=(nx-nz)/(nx-ny) is also calculated.

In this specification, the wavelength at which the refractive index is measured is 550 nm unless otherwise stated.

[EXAMPLE]

The following paragraphs will describe the features of the invention in more detail with reference to examples and comparative examples. Any materials, usage amounts, ratios, details of processing, procedures of processing, etc. shown in the examples may be appropriately modified without departing from the spirit of the present invention. Of course, the scope of the invention should not be interpreted in a limiting manner based on the specific examples presented below.

<Synthesis of the polymerizable liquid crystal compound represented by formula (4)> [Synthesis Example 1]

Compound (1) was synthesized according to the following scheme. Compound (1-I) was prepared according to [0085] to [0087], page 18 of JP 43 97 550 B2 synthesized.

BHT (37 mg) was added to a tetrahydrofuran (THF) solution (20 mL) containing methanesulfonyl chloride (10.22 g) and the internal temperature was cooled to -5 °C. To the mixture, a THF solution (50 mL) containing 1-I (31.5 mmol, 8.33 g) and diisopropylethylamine (17.6 mL) was added dropwise so that the internal temperature did not fall to 0 °C or raised above. The mixture was stirred at -5°C for 30 minutes and diisopropylamine (16.7 mL) and a THF solution (20 mL) containing 1-II and 4-dimethylaminopyridine (DMAP) (a spatula) were added. The mixture was then stirred at room temperature for 4 hours. To the mixture, methanol (5 mL) was added to stop the reaction, and water and ethyl acetate were further added. An organic layer as a result of extraction with ethyl acetate was evaporated using a rotary evaporator to remove the solvent, and the residue was purified by silica gel column chromatography to obtain 1-III.

BHT (3 mg) was added to a THF solution (10 mL) containing methanesulfonyl chloride (355 mg), the internal temperature was cooled to -5 °C. Carboxylic acid 1-IV (404 mg) and diisopropylethylamine (472 pL) were added dropwise to the mixture so that the internal temperature did not rise to 0 °C or above. The mixture was stirred at 5°C for 30 minutes and diisopropylethylamine (472 pL) and a THF solution (2 mL) containing the phenol 1-III (1.0 g) and DMAP (a spatula) were added . The mixture was then stirred at room temperature for 2 hours. Methanol (5 mL) was then added to the mixture to stop the reaction, followed by further addition of water and ethyl acetate. An organic layer as a result of extraction with ethyl acetate was evaporated using a rotary evaporator to remove the solvent to obtain a crude product of compound (1). Purification by silica gel column chromatography gave compound (1) in a yield of 58%. ¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.9-2.0(m,4H), 2.2(s,3H), 2.5(s,3H), 4.1- 4.3(m,4H), 5.8(d,1H), 6.1(dd,1H), 6.4(d,1H), 6.9-7.0(m,2H), 7 ,1-7.2(m,3H), 7.3-7.4(m,2H), 8.1-8.2(m,4H)

The phase transition temperatures of the compound (1) were determined by observing the nature under a polarizing microscope. The transition from the crystal phase to a nematic liquid crystal phase was observed at 83°C, and the transition to the isotropic phase was observed above 135°.

[Synthesis example 2]

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,3(t,3H), 1,9-2,0(m,4H), 2,3(s,3H), 2,7-2,8(m,2H), 4,1-4,3(m,4H), 5,8(d,1H), 6,1(dd,1H), 6,4(d,1H), 6,9-7,0(m,2H), 7,1-7,2(m,3H), 7,3-7,4(m,2H), 8,1-8,2(m,4H)Compound (2) was obtained according to the same synthesis procedure as in Synthesis Example 1 except that p-ethylbenzoic acid was used instead of the carboxylic acid 1-IV. Also, compound (2) showed the same nematic liquid crystallinity as compound (1).

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.3(t,3H), 1.9-2.0(m,4H), 2.3(s,3H), 2.7- 2.8(m,2H), 4.1-4.3(m,4H), 5.8(d,1H), 6.1(dd,1H), 6.4(d,1H), 6 ,9-7.0(m,2H), 7.1-7.2(m,3H), 7.3-7.4(m,2H), 8.1-8.2(m,4H)

[Synthesis example 3]

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,0(t,3H), 1,6-1,8(m,2H), 1,9-2,0(m,4H), 2,3(s,3H), 2,7-2,8(m,2H), 4,1-4,3(m,4H), 5,8(d,1H), 6,1(dd,1H), 6,4(d,1H), 6,9-7,0(m,2H), 7,1-7,2(m,3H), 7,3-7,4(m,2H), 8,1-8,2(m,4H)Compound (3) was obtained according to the same synthesis procedure as in Synthesis Example 1 except that pn-propylbenzoic acid was used instead of carboxylic acid 1-IV. Also, compound (3) showed the same nematic liquid crystallinity as compound (1).

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.0(t,3H), 1.6-1.8(m,2H), 1.9-2.0(m,4H), 2.3(s,3H), 2.7-2.8(m,2H), 4.1-4.3(m,4H), 5.8(d,1H), 6.1(dd, 1H), 6.4(d,1H), 6.9-7.0(m,2H), 7.1-7.2(m,3H), 7.3-7.4(m,2H) , 8.1-8.2(m,4H)

[Synthesis example 4]

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 0,9(t,3H), 1,3-1,5(m,2H), 1,6-1,7(m,2H), 1,9-2,0(m,4H), 2,3(s,3H), 2,7-2,8(m,2H), 4,1-4,3(m,4H), 5, 8 (d, 1H), 6, 1 (dd, 1H), 6,4 (d,1H), 6,9-7,0(m,2H), 7,1-7,2(m,3H), 7,3-7,4(m,2H), 8,1-8,2(m,4H) Compound (4) was obtained according to the same synthesis procedure as in Synthesis Example 1 except that pn-butylbenzoic acid was used instead of carboxylic acid 1-IV. Also, compound (4) showed the same nematic liquid crystallinity as compound (1).

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 0.9(t,3H), 1.3-1.5(m,2H), 1.6-1.7(m,2H), 1.9-2.0(m,4H), 2.3(s,3H), 2.7-2.8(m,2H), 4.1-4.3(m,4H), 5, 8 (d, 1H), 6, 1 (dd, 1H), 6.4 (d,1H), 6.9-7.0(m,2H), 7.1-7.2(m,3H) , 7.3-7.4(m,2H), 8.1-8.2(m,4H)

[Synthesis example 5]

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,9-2,0(m,4H), 2,2(s,3H), 3,9(s,3H),4,1-4,3(m,4H), 5,8(d,1H), 6,1(dd,1H), 6,4(d,1H), 6,9-7,0(m,4H), 7,1-7,2(m,3H), 8,1-8,2(m,4H)Compound (5) was obtained according to the same synthesis procedure as in Synthesis Example 1 except that p-methoxybenzoic acid was used instead of the carboxylic acid 1-IV. Also, compound (5) showed the same nematic liquid crystallinity as compound (1).

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.9-2.0(m,4H), 2.2(s,3H), 3.9(s,3H),4.1- 4.3(m,4H), 5.8(d,1H), 6.1(dd,1H), 6.4(d,1H), 6.9-7.0(m,4H), 7 ,1-7.2(m,3H), 8.1-8.2(m,4H)

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,5(t,3H),1,9-2,0(m,4H), 2,3(s,3H),4,0-4,3(m,6H), 5,8 (d, 1H), 6,1 (dd, 1H), 6,4(d,1H), 6,9-7,0(m,4H), 7,1-7,2(m,3H), 8,1-8,2(m,4H)Compound (6) was obtained according to the same synthesis procedure as in Synthesis Example 1 except that p-ethoxybenzoic acid was used instead of the carboxylic acid 1-IV. Also, compound (6) showed the same nematic liquid crystallinity as compound (1).

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.5(t,3H),1.9-2.0(m,4H), 2.3(s,3H),4.0- 4.3(m,6H), 5.8 (d, 1H), 6.1 (dd, 1H), 6.4(d,1H), 6.9-7.0(m,4H), 7 ,1-7.2(m,3H), 8.1-8.2(m,4H)

[Synthesis example 7]

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,9-2,0(m,4H), 2,3(s,3H), 4,1-4,3(m,4H), 5,8(d,1H), 6,1(dd,1H), 6,4(d,1H), 6,9-7,0(m,2H), 7,1-7,3(m,3H), 7,4-7,5(m,3H), 7,6-7,8(m,4H), 8,1-8,3(m,4H)Compound (7) was obtained according to the same synthesis procedure as in Synthesis Example 1 except that p-phenylbenzoic acid was used instead of the carboxylic acid 1-IV. Also, compound (7) showed the same nematic liquid crystallinity as compound (1).

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.9-2.0(m,4H), 2.3(s,3H), 4.1-4.3(m,4H), 5.8(d,1H), 6.1(dd,1H), 6.4(d,1H), 6.9-7.0(m,2H), 7.1-7.3(m, 3H), 7.4-7.5(m,3H), 7.6-7.8(m,4H), 8.1-8.3(m,4H)

[Synthesis example 8]

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,9-2,0(m,4H), 2,2(s,3H), 3,9(s,3H), 4,1-4,3(m,4H), 5, 8 (d, 1H), 6, 1 (dd, 1H), 6,4-6,6(m,2H), 6,9-7,0(m,4H), 7,1-7,2(m,3H), 7,5-7,6(m,2H), 7,8-7,9(m,1H), 8,1-8,2(m,2H)Compound (8) was obtained according to the same synthesis procedure as in Synthesis Example 1 except that p-methoxycinnamic acid was used instead of the carboxylic acid 1-IV. Also, compound (8) showed the same nematic liquid crystallinity as compound (1).

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.9-2.0(m,4H), 2.2(s,3H), 3.9(s,3H), 4.1- 4.3(m,4H), 5, 8 (d, 1H), 6, 1 (dd, 1H), 6.4-6.6(m,2H), 6.9-7.0(m, 4H), 7.1-7.2(m,3H), 7.5-7.6(m,2H), 7.8-7.9(m,1H), 8.1-8.2( m,2H)

[Synthesis example 9]

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,9-2,0(m,4H), 2,2(s,3H), 4,1-4,3(m,4H), 5,8(d,1H), 6,1(dd,1H), 6,4(d,1H), 6,6-6,7(d,1H), 6,9-7,0(m,4H), 7,1-7,2(m,3H), 7,4-7,5(m,3H), 7,6-7,7(m,2H), 7,9(d,1H), 8,1-8,2(m,2H)Compound (9) was obtained according to the same synthesis procedure as in Synthesis Example 1 except that cinnamic acid was used instead of carboxylic acid 1-IV. Also, compound (9) showed the same nematic liquid crystallinity as compound (1).

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.9-2.0(m,4H), 2.2(s,3H), 4.1-4.3(m,4H), 5.8(d,1H), 6.1(dd,1H), 6.4(d,1H), 6.6-6.7(d,1H), 6.9-7.0(m, 4H), 7.1-7.2(m,3H), 7.4-7.5(m,3H), 7.6-7.7(m,2H), 7.9(d,1H) , 8.1-8.2(m,2H)

[Synthesis example 10]

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,3(t,3H), 2,1-2,3(m,2H), 2,3(s,3H), 2,7-2,8(m,2H), 4,1-4,5(m,4H), 5,8(d,1H), 6,1(dd,1H), 6,4(d,1H), 6,9-7,0(m,2H), 7,1-7,2(m,3H), 7,3-7,4(m,2H), 8,1-8,2(m,4H)Compound (2A) was obtained according to the same synthesis procedure as in Synthesis Example 1 except that compound (1-I) was replaced with compound (1-II) instead of carboxylic acid 1-IV. The compound (1-II) was described with reference to paragraphs [0085] to [0087] on page 18 of JP 43 97 550 B2 synthesized, except that 3-acryloyloxypropanol was used. Compound (2A), like compound (1), was also found to have nematic liquid crystallinity.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.3(t,3H), 2.1-2.3(m,2H), 2.3(s,3H), 2.7- 2.8(m,2H), 4.1-4.5(m,4H), 5.8(d,1H), 6.1(dd,1H), 6.4(d,1H), 6 ,9-7.0(m,2H), 7.1-7.2(m,3H), 7.3-7.4(m,2H), 8.1-8.2(m,4H)

[Synthesis example 11]

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,8-2,0(m,4H), 2,3(s,3H), 4,2-4,5(m,4H), 5, 8 (d, 1H), 6, 1 (dd, 1H), 6,4 (d,1H), 7,1-7,3(m,3H), 7,3-7,4(m,2H), 7,4-7,5(m,3H), 7,6-7,8(m,4H), 8, 1-8, 3 (m, 4H)Compound (7F) (does not fall under formula (4)) was obtained according to the same synthesis procedure as in Synthesis Example 1 except that compound (1-I) was replaced with compound (1-II) instead of carboxylic acid 1-IV. The compound (1-III) was described with reference to paragraph [0185] on page 44 of JP 46 06 195 B2 synthesized procedures described. Compound (7F), like compound (1), was also found to have nematic liquid crystallinity.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.8-2.0(m,4H), 2.3(s,3H), 4.2-4.5(m,4H), 5, 8 (d, 1H), 6, 1 (dd, 1H), 6.4 (d,1H), 7.1-7.3(m,3H), 7.3-7.4(m, 2H), 7.4-7.5(m,3H), 7.6-7.8(m,4H), 8, 1-8, 3 (m, 4H)

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm):1,9-2,0(m,4H), 2,25(s,3H), 4,1-4,3(m,4H), 5,8-5,9(m,2H), 6,1-6,2(m,1H), 6,3-6,5(m,3H), 6,9-7,0(m,2H), 7,1-7,2(m,3H), 7,6-7,7(m,2H), 7,8(s,1H), 8,1-8,2(m,4H)Compound (1L) was synthesized according to the same synthesis procedure as in Synthesis Example 1 except that 4-(acryloylamino)benzoic acid was used instead of carboxylic acid 1-IV. Compound (1L), like compound (1), was also found to have nematic liquid crystallinity.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):1.9-2.0(m,4H), 2.25(s,3H), 4.1-4.3(m,4H), 5.8-5.9(m,2H), 6.1-6.2(m,1H), 6.3-6.5(m,3H), 6.9-7.0(m,2H ), 7.1-7.2(m,3H), 7.6-7.7(m,2H), 7.8(s,1H), 8.1-8.2(m,4H)

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,9-2,0(m,4H), 2,05(s,3H), 2,25(s,3H), 4,1-4,3(m,4H), 5,5(d,1H), 5,8-5,9(m,2H), 6,1(dd,1H), 6,4(d,1H), 6,9-7,0(m,2H), 7,1-7,2(m,3H), 7,7-7,8(m,2H), 8,0(s,1H), 8,1-8,2(m,4H)Compound (2L) was synthesized according to the same synthesis procedure as in Synthesis Example 1 except that 4-(methacryloylamino)benzoic acid was used instead of carboxylic acid 1-IV. Compound (2L), like compound (1), was also found to have nematic liquid crystallinity.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.9-2.0(m,4H), 2.05(s,3H), 2.25(s,3H), 4.1- 4.3(m,4H), 5.5(d,1H), 5.8-5.9(m,2H), 6.1(dd,1H), 6.4(d,1H), 6 ,9-7.0(m,2H), 7.1-7.2(m,3H), 7.7-7.8(m,2H), 8.0(s,1H), 8.1 -8.2(m,4H)

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,9-2,0(m,4H), 2,25 (s, 3H), 4,1-4,3(m,4H), 4,7(m,2H), 5,25-5,45 (m, 2H), 5, 8 (d, 1H), 5,9-6,0 (m,1H), 6,15(dd,1H), 6,4 (d,1H), 6, 9-7,0(m,2H), 7,1-7,2(m,3H), 7,4(m,1H), 7,45-7,55 (m, 2H), 8, 1-8,2(m,4H)Compound (3L) (does not fall under formula (4)) was synthesized according to the same synthesis procedure as in Synthesis Example 1 except that 4-(allyloxycarbamoyl)benzoic acid was used instead of carboxylic acid 1-IV. Compound (3L), like compound (1), was also found to have nematic liquid crystallinity.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.9-2.0(m,4H), 2.25 (s, 3H), 4.1-4.3(m,4H), 4.7(m,2H), 5.25-5.45 (m, 2H), 5, 8 (d, 1H), 5.9-6.0 (m,1H), 6.15(dd, 1H), 6.4 (d,1H), 6, 9-7.0(m,2H), 7.1-7.2(m,3H), 7.4(m,1H), 7.45 -7.55 (m, 2H), 8, 1-8.2 (m, 4H)

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,9-2,0(m,4H), 2,25(s,3H),4,1-4,3(m,4H), 4,65(m,2H), 5,3-5,5(m,2H), 5,8(d,1H), 6,0-6,1(m,1H), 6,15(dd,1H), 6,4 (d,1H), 6,9-7,0(m,4H), 7,1-7,2(m,3H), 8,1-8,2(m,4H)Compound (4L) was synthesized according to the same synthesis procedure as in Synthesis Example 1 except that 4-allyloxybenzoic acid was used instead of carboxylic acid 1-IV. Compound (4L), like compound (1), was also found to have nematic liquid crystallinity.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.9-2.0(m,4H), 2.25(s,3H),4.1-4.3(m,4H), 4.65(m,2H), 5.3-5.5(m,2H), 5.8(d,1H), 6.0-6.1(m,1H), 6.15(dd, 1H), 6.4 (d,1H), 6.9-7.0(m,4H), 7.1-7.2(m,3H), 8.1-8.2(m,4H)

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,9-2,0(m,4H), 2,0(s,3H), 2,25(s,3H), 3,6-3,7(m,2H), 4,1-4,4(m,6H), 5,4(bd,1H), 5,65(d,1H), 5,8-5,9(d,2H), 6,15(dd,1H), 6,4(d,1H), 6,9-7,0(m,4H), 7,1-7,2(m,3H), 8,1-8,2(m,4H)Compound (7L) (does not fall under formula (4)) was synthesized according to the same synthesis procedure as in Synthesis Example 1 except that 4-[N-(2-methacryloyloxyethyl)carbamoyloxy]benzoic acid was used instead of carboxylic acid 1-IV. Compound (7L), like compound (1), was also found to have nematic liquid crystallinity.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.9-2.0(m,4H), 2.0(s,3H), 2.25(s,3H), 3.6- 3.7(m,2H), 4.1-4.4(m,6H), 5.4(w,1H), 5.65(d,1H), 5.8-5.9(d, 2H), 6.15(dd,1H), 6.4(d,1H), 6.9-7.0(m,4H), 7.1-7.2(m,3H), 8.1 -8.2(m,4H)

¹H-NMR (Lösungsmittel: CDCl₃) δ(ppm): 1,8-2,0(m,8H), 2,3(s,3H), 4,2-4,5 (m, 8H), 5,8(m,2H), 6,1(m,2H), 6,4(m,2H), 6,9-7,0(m,4H), 7,1-7,2(m,3H),7,3-7,4(m,2H), 8,1-8,2(m,4H), 8,2-8,3(m,2H)Compound (8L) was obtained according to the same synthesis procedure as in Synthesis Example 1 except that the carboxylic acid (V-29) described with reference to paragraph [0082] of JP 2013- 067 603 A was synthesized, was used instead of carboxylic acid 1-IV. Compound (8L), like compound (1), was also found to have nematic liquid crystallinity.

¹ H-NMR (solvent: CDCl ₃ ) δ(ppm): 1.8-2.0(m,8H), 2.3(s,3H), 4.2-4.5 (m, 8H), 5.8(m,2H), 6.1(m,2H), 6.4(m,2H), 6.9-7.0(m,4H), 7.1-7.2(m, 3H),7.3-7.4(m,2H), 8.1-8.2(m,4H), 8.2-8.3(m,2H)

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,8-2,0(m,6H), 2,3(s,3H), 4,2-4,5(m,8H), 5,8(m,2H), 6,1(m,2H), 6,4(m,2H), 6,9-7,0(m,4H), 7,1-7,2(m,3H),7,3-7,4(m,2H), 8,1-8,2(m,4H), 8,2-8,3(m,2H)Compound (1N) was obtained according to the same synthesis procedure as in Synthesis Example 1 except that the carboxylic acid (V-32) described with reference to paragraph [0082] of JP 2013- 067 603 A was synthesized, was used instead of carboxylic acid 1-IV. Compound (1N), like compound (1), was also found to have nematic liquid crystallinity.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.8-2.0(m,6H), 2.3(s,3H), 4.2-4.5(m,8H), 5.8(m,2H), 6.1(m,2H), 6.4(m,2H), 6.9-7.0(m,4H), 7.1-7.2(m, 3H),7.3-7.4(m,2H), 8.1-8.2(m,4H), 8.2-8.3(m,2H)

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,9-2,0(m,4H), 2,0(s,3H), 2,25(s,3H), 4,1-4,5(m,8H), 5,65(d,1H), 5,8-5,9(m,2H), 6,15(dd,1H), 6,4 (d,1H), 6,9-7,0(m,4H), 7,1-7,2(m,3H), 7,3-7,4(m,2H), 8,1-8,2(m,4H), 8,2-8,3(m,2H) Compound (2N) was obtained according to the same synthesis procedure as in Synthesis Example 1 except that the carboxylic acid (V-31) described with reference to paragraph [0082] of JP 2013- 067 603 A was synthesized, was used instead of carboxylic acid 1-IV. Compound (2N), like compound (1), was also found to have nematic liquid crystallinity.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.9-2.0(m,4H), 2.0(s,3H), 2.25(s,3H), 4.1- 4.5(m,8H), 5.65(d,1H), 5.8-5.9(m,2H), 6.15(dd,1H), 6.4 (d,1H), 6 ,9-7.0(m,4H), 7.1-7.2(m,3H), 7.3-7.4(m,2H), 8.1-8.2(m,4H) , 8.2-8.3(m,2H)

<Synthesis of the liquid crystal compound represented by formula (5) used in the present invention>

[Synthesis example 12]

Compound (11) was synthesized according to the following scheme.

BHT (37 mg) was added to an ethyl acetate solution (14.2 mL) containing methanesulfonyl chloride (3.95 g, 34.5 mmol) and the internal temperature was reduced to -5 °C. To the contents, a THF solution (9 mL) containing p-toloylic acid (32.9 mm, 4.48 g) and triethylamine (4.9 mL) was added dropwise so that the internal temperature did not drop to 0 °C or raised above. The contents were stirred at -5°C for 30 minutes, then an ethyl acetate solution (10 mL) containing 1-II (2.0 g) and DMAP (a full spatula) and triethylamine (4.9 mL) was added dropwise over 15 minutes. The contents were stirred at room temperature for 4 hours. The reaction was stopped by adding methanol and water, and the precipitate was collected by filtration to obtain a crude product of compound (11). The crude product was purified by silica gel column chromatography to obtain compound (11) in a yield of 76%. ¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 2.2(s,3H), 2.5(s,6H), 7.0-7.2(m,3H), 7.3-7.4( m,4H), 8.1-8.2(m,4H)

[Synthesis example 13]

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,3(t,6H), 2,3(s,3H), 2,7-2,8(m,4H), 7,0-7,2(m,3H), 7,3-7,4(m,4H), 8,1-8,2(m,4H)Compound (12) was obtained according to the same synthesis procedure as in Synthesis Example 12 except that p-ethylbenzoic acid was used instead of p-toloy acid.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.3(t,6H), 2.3(s,3H), 2.7-2.8(m,4H), 7.0- 7.2(m,3H), 7.3-7.4(m,4H), 8.1-8.2(m,4H)

[Synthesis example 14]

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,0(t,6H), 1,6-1,8(m,4H), 2,3(s,3H), 2,7-2,8(m,4H), 7,0-7,2(m,3H), 7,3-7,4(m,4H), 8,1-8,2(m,4H)Compound (13) was obtained according to the same synthesis procedure as in Synthesis Example 12 except that pn-propylbenzoic acid was used instead of p-toloylic acid.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.0(t,6H), 1.6-1.8(m,4H), 2.3(s,3H), 2.7- 2.8(m,4H), 7.0-7.2(m,3H), 7.3-7.4(m,4H), 8.1-8.2(m,4H)

[Synthesis example 15]

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 0,9(t,6H), 1,3-1,5(m,4H), 1,6-1,7(m,H), 2,3(s,3H), 2,7-2,8(m,4H), 7,0-7,2(m,3H), 7,3-7,4(m,4H), 8,1-8,2(m,4H)Compound (14) was obtained according to the same synthesis procedure as in Synthesis Example 12 except that pn-butylbenzoic acid was used instead of p-toloylic acid.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 0.9(t,6H), 1.3-1.5(m,4H), 1.6-1.7(m,H), 2.3(s,3H), 2.7-2.8(m,4H), 7.0-7.2(m,3H), 7.3-7.4(m,4H), 8, 1-8.2(m,4H)

[Synthesis example 16]

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 2,2(s,3H), 3,9(s,6H), 6,9-7,0(m,4H), 7,0-7,2(m,3H), 8,1-8,2(m,4H)Compound (15) was obtained according to the same synthesis procedure as in Synthesis Example 12 except that p-methoxybenzoic acid was used instead of p-toloy acid.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 2.2(s,3H), 3.9(s,6H), 6.9-7.0(m,4H), 7.0- 7.2(m,3H), 8.1-8.2(m,4H)

[Synthesis example 17]

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,5(t,6H), 2,3(s,3H), 4,0-4,3(m,4H), 6,9-7,0(m,4H), 7,0-7,2(m,3H), 8,1-8,2(m,4H)Compound (16) was obtained according to the same synthesis procedure as in Synthesis Example 12 except that p-ethoxybenzoic acid was used instead of p-toloy acid.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.5(t,6H), 2.3(s,3H), 4.0-4.3(m,4H), 6.9- 7.0(m,4H), 7.0-7.2(m,3H), 8.1-8.2(m,4H)

[Synthesis example 18]

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 2,3(s,3H), 7,1-7,3(m,3H), 7,4-7,5 (m,6H), 7,6-7,8(m,8H), 8,1-8,3(m,4H)Compound (17) was obtained according to the same synthesis procedure as in Synthesis Example 12 except that p-phenylbenzoic acid was used instead of p-toloy acid.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 2.3(s,3H), 7.1-7.3(m,3H), 7.4-7.5 (m,6H), 7.6-7.8(m,8H), 8.1-8.3(m,4H)

[Synthesis example 19]

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 2,2(s,3H), 3,9(s,6H), 5,8(d,1H), 6,1(dd,1H), 6,4-6,6(m,2H), 6,9-7,0(m,4H), 7,1-7,2(m,3H), 7,5-7,6(m,2H), 7,8-7,9(m,1H), 8,1-8,2(m,2H)Compound (18) was obtained according to the same synthesis procedure as in Synthesis Example 12 except that p-methoxycinnamic acid was used instead of p-toloy acid.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 2.2(s,3H), 3.9(s,6H), 5.8(d,1H), 6.1(dd,1H) , 6.4-6.6(m,2H), 6.9-7.0(m,4H), 7.1-7.2(m,3H), 7.5-7.6(m, 2H), 7.8-7.9(m,1H), 8.1-8.2(m,2H)

[Synthesis example 20]

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,9-2,0(m,4H), 2,2(s,3H), 4,1-4,3(m,4H), 5,8(d,1H), 6,1(dd,1H), 6,4(d,1H), 6,6-6,7(d,1H), 6,9-7,0(m,4H), 7,1-7,2(m,3H), 7,4-7,5(m,3H), 7,6-7,7(m,2H), 7,9(d,1H), 8,1-8,2(m,2H)Compound (19) was obtained according to the same synthesis procedure as in Synthesis Example 12 except that cinnamic acid was used instead of p-toloy acid.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.9-2.0(m,4H), 2.2(s,3H), 4.1-4.3(m,4H), 5.8(d,1H), 6.1(dd,1H), 6.4(d,1H), 6.6-6.7(d,1H), 6.9-7.0(m, 4H), 7.1-7.2(m,3H), 7.4-7.5(m,3H), 7.6-7.7(m,2H), 7.9(d,1H) , 8.1-8.2(m,2H)

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 2,25 (s,3H), 5,8-5,9(m,2H), 6,3-6,5(m,4H), 7,1-7,2(m,3H), 7,6-7,7(m,4H), 7,8(s,2H), 8,1-8,2(m,4H)Compound (11L) was obtained according to the same synthesis procedure as in Synthesis Example 12 except that 4-(acryloylamino)benzoic acid was used instead of p-toloylic acid.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 2.25 (s,3H), 5.8-5.9(m,2H), 6.3-6.5(m,4H), 7.1-7.2(m,3H), 7.6-7.7(m,4H), 7.8(s,2H), 8.1-8.2(m,4H)

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 2,05(s,6H), 2,25 (s,3H), 5,5(d,2H), 5,8-5,9(d,2H), 7,1-7,2(m,3H), 7,7-7,8(m,4H), 8,0(s,2H), 8,1-8,2(m, 4H)Compound (12L) was obtained according to the same synthesis procedure as in Synthesis Example 12 except that 4-(methacryloylamino)benzoic acid was used instead of p-toloy acid.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 2.05(s,6H), 2.25 (s,3H), 5.5(d,2H), 5.8-5.9( d,2H), 7.1-7.2(m,3H), 7.7-7.8(m,4H), 8.0(s,2H), 8.1-8.2(m, 4H)

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 2,25(s,3H), 4,7(m,4H), 5,25-5,45(m,4H), 5,9-6,0(m,2H), 7,1-7,2(m,3H), 7,4(m,2H), 7,45-7,55(m,4H), 8,1-8,2(m,4H)Compound (13L) (does not fall under formula (5)) was obtained according to the same synthesis procedure as in Synthesis Example 12 except that 4-(allyloxycarbamoyl)benzoic acid was used instead of p-toloylic acid.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 2.25(s,3H), 4.7(m,4H), 5.25-5.45(m,4H), 5.9- 6.0(m,2H), 7.1-7.2(m,3H), 7.4(m,2H), 7.45-7.55(m,4H), 8.1-8, 2(m,4H)

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 2,25(s,3H), 4,65(m,4H), 5,3-5,5(m,4H), 6,0-6,1(m,2H), 6,9-7,0(m,4H), 7,1-7,2(m,3H), 8,1-8,2(m,4H)Compound (14L) was obtained according to the same synthesis procedure as in Synthesis Example 12 except that 4-allyloxybenzoic acid was used instead of p-toloy acid.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 2.25(s,3H), 4.65(m,4H), 5.3-5.5(m,4H), 6.0- 6.1(m,2H), 6.9-7.0(m,4H), 7.1-7.2(m,3H), 8.1-8.2(m,4H)

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 2,0(s,6H), 2,25 (s,3H), 3,6-3,7(m,4H), 4,1-4,4(m,4H), 5,4(bd,2H), 5,65(d,2H), 5,8-5,9(d,2H), 6,9-7,0(m,4H), 7,1-7,2(m,3H), 8,1-8,2(m,4H)Compound (17L) (does not fall under formula (5)) was obtained according to the same synthesis procedure as in Synthesis Example 12 except that 4-[N-(2-methacryloyloxyethyl)carbamoyloxy]benzoic acid was used instead of p-toloylic acid.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 2.0(s,6H), 2.25 (s,3H), 3.6-3.7(m,4H), 4.1- 4.4(m,4H), 5.4(w,2H), 5.65(d,2H), 5.8-5.9(d,2H), 6.9-7.0(m, 4H), 7.1-7.2(m,3H), 8.1-8.2(m,4H)

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,8-2,0(m,8H), 2,3(s,3H), 4,2-4,5(m,8H), 5,8(m,2H), 6,1(m,2H), 6,4(m,2H), 6,9-7,0(m,4H), 7,1-7,2(m,3H), 7,3-7,4(m,4H), 8,1-8,2(m,4H), 8,2-8,3(m,4H)Compound (11M) was obtained according to the same synthesis method as in Synthesis Example 12 except that the carboxylic acid (V-29) described with reference to [0082] of JP 2013- 067 603 A was synthesized, was used instead of p-toloylic acid.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.8-2.0(m,8H), 2.3(s,3H), 4.2-4.5(m,8H), 5.8(m,2H), 6.1(m,2H), 6.4(m,2H), 6.9-7.0(m,4H), 7.1-7.2(m, 3H), 7.3-7.4(m,4H), 8.1-8.2(m,4H), 8.2-8.3(m,4H)

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 2,0 (s,6H), 2,25 (s,3H), 4,1-4,5(m,8H), 5,65 (d, 2H), 5,8-5,9(m,2H), 6,9-7,0(m,4H),7,1-7,2(m,3H), 7,3-7,4(m,4H), 8,1-8,2(m,4H), 8,2-8,3(m,4H)Compound (14M) was obtained according to the same synthesis method as in Synthesis Example 12 except that the carboxylic acid (V-31) described with reference to [0082] of JP 2013- 067 603 A was synthesized, was used instead of p-toloylic acid.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 2.0 (s,6H), 2.25 (s,3H), 4.1-4.5(m,8H), 5.65 ( d, 2H), 5.8-5.9(m,2H), 6.9-7.0(m,4H),7.1-7.2(m,3H), 7.3-7, 4(m,4H), 8.1-8.2(m,4H), 8.2-8.3(m,4H)

¹H-NMR (Lösungsmittel: CDCl₃) δ (ppm): 1,8-2,0(m,4H), 2,3(s,3H), 4,2-4,5(m,8H), 5,8(m,2H), 6,1(m,2H), 6,4(m,2H), 6,9-7,0(m,4H), 7,1-7,2(m,3H), 7,3-7,4(m,4H), 8,1-8,2(m,4H), 8,2-8,3(m,4H)Compound (15M) was obtained according to the same synthesis method as in Synthesis Example 12 except that the carboxylic acid (V-32) described with reference to [0082] of JP 2013- 067 603 A was synthesized, was used instead of p-toloylic acid.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.8-2.0(m,4H), 2.3(s,3H), 4.2-4.5(m,8H), 5.8(m,2H), 6.1(m,2H), 6.4(m,2H), 6.9-7.0(m,4H), 7.1-7.2(m, 3H), 7.3-7.4(m,4H), 8.1-8.2(m,4H), 8.2-8.3(m,4H)

[Example 1]

A mixture of compounds (1), (11) and (1-A) was obtained according to the following scheme.

Compound (1-I) (106.1 g, 401.3 mmol) and p-toloylic acid (6.07 g, 44.6 mmol) were treated with ethyl acetate (100 mL), tetrahydrofuran (100 mL) and triethylamine (83, 6 mL) mixed. The solution obtained became long sam added dropwise to an ethyl acetate solution containing methanesulfonyl chloride (50.8 g, 443.7 mmol) while cooling on ice.

The mixture was then stirred while cooling on ice for 1 hour, an ethyl acetate solution of compound (1-II) was added dropwise while cooling on ice, and then triethylamine (67.3 mL) was slowly added dropwise while cooling on ice.

The resulting mixture was then stirred for 2 hours while maintaining the reaction temperature at 20°C and then water (60 g) was added to allow extraction into an organic layer and the organic layer was diluted with 2% aqueous Hydrochloric acid solution and then washed with a 10% aqueous sodium chloride solution.

The organic layer was filtered under suction, methanol/water was added to the filtrate so that crystals were deposited, and the deposited crystals were collected by filtration to obtain a liquid crystal composition containing a mixture of compounds (1), (11) and ( 1-A) contained (yield = 107.7 g).

The mass contents of the compounds (1), (11) and (1-A) in the liquid crystal composition thus obtained were 8.3%, 0.7% and 91%, respectively.

[Example 2]

<Preparation of liquid crystal composition>

Using the compound (1) synthesized in Synthesis Example 1, the compound (11) synthesized in Synthesis Example 12, and the polymerizable liquid crystal compound (1-A), a liquid crystal composition was prepared according to the method described below.

A liquid crystal composition coating liquid (A) having the following composition was prepared as a liquid crystal composition according to Example 2. Polymerizable liquid crystal compound (1) of formula (4) 15 parts by mass Liquid crystal compound (11) of formula (5) 2 mass parts Polymerizable liquid crystal compound (1-A) represented by formula (6) 85 parts by mass Methyl ethyl ketone 238 parts by mass

<Filmmaking>

Next, using the thus obtained liquid crystal composition according to Example 2, a film according to Example 2 was prepared according to the method described below.

A polyimide alignment film SE-130 from Nissan Chemical Industries Ltd. was coated over a cleaned glass substrate. spin-coated, the coating was dried and baked at 250 ° C for one hour. The obtained alignment film was rubbed, thereby producing a substrate having an alignment film. Over the rubbed surface of the alignment film on the substrate, the liquid crystal composition coating liquid was spin-coated as the liquid crystal composition according to Example 2 at room temperature. The coating formed on the rubbed surface of the alignment film on the substrate was allowed to stand at room temperature for 30 minutes, thereby forming the film according to Example 2.

(Evaluation of suppression of crystallization)

It was found that the liquid crystal film thus obtained had a crystal deposition rate of 10% when visually observed in an arbitrary area thereof under a polarizing microscope.

[Examples 3 to 14, Examples 42 to 53 and Comparative Examples 1 to 6]

Liquid crystal composition coating liquids were prepared in the same manner as in Example 2 except that compounds (1) and (1-A) prepared in Example 1 were replaced with the compounds shown in Table 1 below to prepare liquid crystal compositions of each To produce examples and comparative examples.

The films according to the individual examples and comparative examples were prepared in the same manner as in Example 2, except that the liquid crystal composition according to Example 2 was replaced with the liquid crystal compositions of the individual examples and comparative examples.

The crystal deposition rate for the thus obtained films of each example and comparative example was measured. The results are summarized in Table 1. In the table, the “polymerizable liquid crystal compound according to formula (4)” is a compound represented by the above-described formula (4), and preferably a polymerizable liquid crystal compound having a (meth)acrylate group. The “liquid crystal compound of formula (5)” is a compound represented by formula (5) described above, and preferably a liquid crystal compound not having a (meth)acrylate group. The “polymerizable liquid crystal compound of formula (6)” is a compound represented by formula (6) described above, preferably a polymerizable liquid crystal compound having two (meth)acrylate groups. [Table 1] Polymerizable liquid crystal compound of formula (4) Liquid crystal compound of formula (5) Polymerizable liquid crystal compound of formula (6) Evaluation of the crystal deposition of the film Example 2 Compound (1) 15 parts by weight Connection (11) 2 parts by weight Compound (1-A) 85 parts by weight A Example 3 Compound (2) 15 parts by weight Connection (12) 2 parts by weight Compound(1-A) 85 parts by weight A Example 4 Compound (3) 15 parts by weight Connection (13) 2 parts by weight Compound(1-A) 85 parts by weight b Example 5 Compound (4) 15 parts by weight Connection (14) 2 parts by weight Compound(1-A) 85 parts by weight b Example 6 Compound (5) 15 parts by weight Connection (15) 2 parts by weight Compound(1-A) 85 parts by weight A(S) Example 7 Compound (6) 15 parts by weight Compound 16) 2 parts by weight Compound(1-A) 85 parts by weight A(S) Example 8 Compound (7) 15 parts by weight Connection (17) 2 parts by weight Compound(1-A) 85 parts by weight A(S) Example 9 Compound 8) 15 parts by weight Connection (18) 2 parts by weight Compound(1-A) 85 parts by weight b Example 10 Compound(9) 15 parts by weight Connection (19) 2 parts by weight Compound(1-A) 85 parts by weight b Example 11 Compound(1) 15 parts by weight Connection (17) 2 parts by weight Compound(1-A) 85 parts by weight b Example 12 Compound(2) 15 parts by weight Connection (17) 2 parts by weight Compound(1-A) 85 parts by weight A Example 13 Compound(2A) 15 parts by weight Connection (12) 2 parts by weight Compound(1-B) 85 parts by weight A(S) [Table 1 (continued)] Polymerizable liquid crystal compound of formula (4) Liquid crystal compound of formula (5) Polymerizable liquid crystal compound of formula (6) Evaluation of the crystal deposition of the film Example 14* Compound (7F) 15 parts by weight Connection (17) 2 parts by weight Compound (1-C) 85 parts by weight A(S) Example 42 Compound (1L) 10 parts by weight Compound (11L) 1 part by weight Compound(1-A) 91 parts by weight A(S) Example 43 Compound (1L) 15 parts by weight Compound (11L) 2 parts by weight Compound(1-A) 85 parts by weight A(S) Example 44 Compound (1L) 20 parts by weight Compound (11L) 3 parts by weight Compound(1-A) 79 parts by weight A(S) Example 45 Compound (1L) 5.3 parts by weight Compound (11L) 0.2 parts by weight Compound(1-A) 96.5 parts by weight A Example 46 Compound (2L) 12 parts by weight Compound 12L) 1 part by weight Compound(1-A) 89 parts by weight A(S) Example 47* Compound (3L) 15 parts by weight Connection (13L) 2 parts by weight Compound(1-A) 85 parts by weight b Example 48 Compound 4L) 18 parts by weight Connection (14L) 2 parts by weight Compound(1-A) 82 parts by weight A Example 49* Compound (7L) 14 parts by weight Connection (17L) 2 parts by weight Compound(1-A) 86 parts by weight A Example 50 Compound (8L) 13 parts by weight Compound (11M) 1 part by weight Compound(1-A) 88 parts by weight A(S) Example 51 Compound(8L) 15 parts by weight Connection (11M) 2 parts by weight Compound(1-A) 85 parts by weight A(S) Example 52 Compound(1N) 15 parts by weight Connection (15M) 2 parts by weight Compound(1-B) 85 parts by weight A(S) Example 53 Compound (2N) 15 parts by weight Connection (14M) 2 parts by weight Compound (1-A) 85 parts by weight A(S) * Reference example (not covered by the wording of the claims) [Table 1 (continued)] Polymerizable liquid crystal compound of formula (4) Liquid crystal compound of formula (5) Polymerizable liquid crystal compound of formula (6) Evaluation of the crystal deposition of the film Comparative example 1 Compound (1-A) 102 parts by weight D Comparative example 2 - - Compound (1-B) 102 parts by weight D Comparative example 3 Compound (1) 17 parts by weight - Compound(1-A) 85 parts by weight C Comparative example 4 Compound (11L) 2 parts by weight Compound (17) 2 parts by weight Compound(1-A) 98 parts by weight D Comparative example 5 Comparative example compound (1') 17 parts by weight - Compound(1-A) 85 parts by weight D Comparative example 6 Comparative example compound (2') 17 parts by weight - Compound(1-A) 85 parts by weight D

The crystal deposition rate in Table 1 was the visually observed area of crystal deposition and was ranked. When the area of crystal deposition was 5% or less of the film, the film was rated at “A(S)”. If the area exceeded 5% and was less than 15%, the film was rated “A”. If the area exceeded 15% and was less than 30%, the film was rated “B”. If the area exceeded 30% and was less than 50%, the film was rated “C”. If the area exceeds 50%, the film was rated “D”.

The structures of compound (1-B) and compound (1-C) in Table 1 are shown below. The structures of the comparison compounds (1') and (2') in Table 1 are also shown below. It should be noted that the comparison compound (1 ') has an in JP 2002-536 529 A is a compound described and the comparison compound (2 ') is a compound described in Molecular Crystals and Liquid Crystals (2010), 530, 169-174.

From the results of Examples 2 to 14, Examples 42 to 53 and Comparative Examples 1 to 6 summarized in Table 1, it was illustrated that the mixture of the polymerizable liquid crystal compound represented by Formula (4) was that represented by Formula (5). Liquid crystal ver bonding and the polymerizable liquid crystal compound represented by formula (1-A) could largely suppress the crystal deposition of the polymerizable liquid crystal compound (1-A).

In particular, a combination of compounds with similar backbones, such as compound (1) and compound (11), was found to improve the suppression effects on crystal deposition.

From the results of Examples 2 to 14 summarized in Table 1, it was found that among the polymerizable liquid crystal compounds represented by formula (4), (1) to (9) and (2A) used for this invention and the polymerizable liquid crystal compound (7F), which does not fall under formula (4)), in particular the compounds (1), (2), (5), (6), (7), (2A) and (7F) have high suppression effects on crystal deposition showed. Furthermore, it was found that among them, compounds (5), (6), (7), (2A) and (7F) exhibited high suppressing effects on crystal deposition. Without being bound by theory, it is believed that compound (7) exhibited a large suppressing effect on crystal deposition because the crystal form of the liquid crystal composition upon deposition was a crystal form which is not easy to be deposited.

From the results of Examples 42 to 53 summarized in Table 1, it was found that among the polymerizable liquid crystal compounds (1L) to (4L), (8L), (1N) and (2N) represented by formula (4), those in this invention are used, and the polymerizable liquid crystal compound (7L) which does not fall under formula (4), in particular the compounds (1L), (2L), (4L), (7L), (8L), (1N) and (2N) showed high suppression effects on crystal deposition. Furthermore, it was found that among them, compounds (1L), (2L), (8L), (1N) and (2N) exhibited strong suppressing effects on crystal deposition.

<Preparation of a selective reflection film>

[Example 15]

The liquid crystal composition (B) was prepared using the compound (1), the compound (11) and the polymerizable liquid crystal compound (1-A) according to the method described below. Polymerizable liquid crystal compound (1) of formula (4) 18 mass parts Liquid crystal compound (11) of formula (5) 2 mass parts Polymerizable liquid crystal compound (11-A) represented by formula (6) 80 parts by mass Chiral agent “Paliocolor LC756” (from BASF) 3 mass parts Air interface side alignment means (X1-1) 0.04 parts by mass Polymerization initiator “Irgacure 819” (from BASF) 3 mass parts Chloroform (solvent) 300 parts by mass

Air interface side alignment means (X1-1)

Over the surface of the alignment film of an alignment film substrate prepared in the same manner as in Example 2, a liquid crystal composition (B) was spin-coated at room temperature, ripened at 120°C for 3 minutes for alignment, exposed to UV using a high-pressure Mercury lamp with a short wavelength component cutoff was irradiated at room temperature for 10 seconds to fix the orientation, thereby obtaining a selective reflection film. Crystal deposition was not observed during a period after coating and before heating.

The obtained selective reflection film was observed under a polarizing microscope, and thus uniform alignment without alignment defect was confirmed. The film was further subjected to transmission spectrometry using a spectrophotometer UV-3100PC from Shimadzu Corporation, whereby a selective reflection peak in the infrared region was observed.

[Examples 16 to 23]

Liquid crystal composition coating liquids were prepared in the same manner as in Example 15 except that Compound (1) was replaced by Compound (2) to Compound (9) and Compound (11) was replaced by Compound (12) to Compound (9). 19) was replaced. The selective reflection film was formed using each of the coating liquids in the same manner as in Example 15. It was found that all selective reflection films showed good alignment. Transmission spectrometry for each of the films, measured using a UV-3100PC spectrophotometer, showed a selective reflectance peak in the infrared region.

[Examples 54 to 66]

Liquid crystal compound coating liquids were prepared in the same manner as in Example 15, except that the composition prepared using Compound (1), Compound (11) and Compound (1-A) was replaced by that in Examples 42 to 15 53 prepared liquid crystal compositions were replaced. The selective reflection films were formed using the respective coating liquids in the same manner as in Example 15. It was found that all selective reflection films showed good alignment. Transmission spectrometry for each of the films, measured using a UV-3100PC spectrophotometer, showed a selective reflectance peak in the infrared region.

[Example 24]

<Production of an optical compensation film (1)>

The liquid crystal composition coating liquid (C) was prepared using the compounds (1), (11) and (1-A) according to the method described below. Polymerizable liquid crystal compound (1) of formula (4) 15 parts by mass Liquid crystal compound (11) of formula (5) 2 mass parts Polymerizable liquid crystal compound (1-A) represented by formula (6) 85 parts by mass Polymerization initiator “Irgacure 819” (from BASF) 3 mass parts Air interface side alignment means (X1-2) 0.1 parts by mass Methyl Ethyl Ketone (Solvent) Air Interface Side Alignment Agent (X1-2) 400 parts by mass

A polyimide alignment film SE-130 from Nissan Chemical Industries Ltd. was coated over a cleaned glass substrate. spin-coated, the coating was dried and baked at 250 ° C for one hour. The obtained film was rubbed to prepare a substrate with an alignment film. Over the surface of the substrate, the coating liquid (C) of a liquid crystal composition was spin-coated at room temperature so that the thickness of the coating layer was controlled to 1 µm, the coated film was ripened at 60 ° C for 1 minute for alignment using a high pressure -Mercury lamp with short wavelength component cut-off was irradiated by UV at room temperature for 10 seconds to fix the alignment, thereby obtaining an optical compensation film. No crystal deposition was observed in the coated film during a period after coating and before heating.

The optical compensation film thus obtained was observed under a polarizing microscope to observe uniform alignment without alignment defect.

Next, the optical compensation film thus obtained was measured for retardation (Re) using AxoScan (Müller Matrix Polarimeter) from Axometrics, Inc. Re(550) at 550 nm was found to be 162.4 nm.

[Examples 25 to 32]

Liquid crystal composition coating liquids were prepared in the same manner as in Example 24 except that Compound (1) was replaced by Compound (2) to Compound (9) and Compound (11) was replaced by Compound (12) to Compound (9). 19) was replaced. Optical compensation films were prepared in the same manner as in Example 24 using the respective coating liquids. The optical compensation films thus obtained were each observed under a polarizing microscope to determine uniform alignment without alignment defects. The Re measurements at 550 nm of the individual optical compensation films are summarized below. [Table 2] Polymerizable liquid crystal compound of formula (4) Liquid crystal compound of formula (5) Polymerizable liquid crystal compound of formula (6) Re (nm) Film thickness (µm) (15 parts by weight (2 parts by weight) (85 parts by weight) Example 24 connection(1) connection(11) Connection(1-A) 161.8 1.01 Example 25 connection(2) connection(12) Connection(1-A) 162.0 1.00 Example 26 connection(3) connection(13) Connection(1-A) 164.3 1.02 Example 27 connection(4) connection(14) Connection(1-A) 162.7 1.02 Example 28 connection(5) connection(15) Connection(1-A) 165.7 0.99 Example 29 connection(6) connection(16) Connection(1-A) 166.1 1.02 Example 30 connection(7) connection(17) Connection(1-A) 180.8 1.02 Example 31 connection(8) connection(18) Connection(1-A) 182.1 1.01 Example 32 connection(9) connection (19) Connection (1-A) 159.2 1.00

[Examples 67 to 74]

Liquid crystal compound coating liquids were prepared in the same manner as in Example 24 except that Compound (1), Compound (11) and Compound (1-A) were replaced with the compounds summarized in the following table. Optical compensation films were formed in the same manner as in Example 24 using the respective coating liquids. The optical compensation films thus obtained were observed under a polarizing microscope to find uniform alignment without alignment defects. The Re measurements at 550 nm of the individual optical compensation films are summarized below. [Table 3] Polymerizable liquid crystal compound of formula (4) (15 parts by weight Liquid crystal compound of formula (5) (2 parts by weight) Polymerizable liquid crystal compound of formula (6) (85 parts by weight) Re (nm) Film thickness (µm) Example 67 Compound (1L) Connection (11L) Connection(1-A) 178.8 1.00 Example 68 Connection (2L) Connection (12L) Connection(1-A) 163.5 1.01 Example 69* Connection (3L) Connection (13L) Connection(1-A) 172.5 0.99 Example 70 Connection (4L) Connection (14L) Connection(1-A) 159.2 1.02 Example 71* Connection (7L) Connection (17L) Connection(1-A) 132.0 0.99 Example 72 Connection (8L) Connection (11M) Connection(1-A) 181.8 1.00 Example 73 Connection (1N) Connection (15M) Connection(1-B) 182.0 1.02 Example 74 Connection (2N) Connection (14M) Connection(1-A) 179.1 1.00 * Reference example (not covered by the wording of the claims)

[Example 33]

<Production of an optical compensation film (2)>

The liquid crystal composition coating liquid (D) was prepared using the compounds (1), (11) and (1-A) according to the method described below. Monofunctional polymerizable compound (1) 15 parts by mass Non-polymerizable compound (11) 2 mass parts Bifunctional polymerizable compound 85 parts by mass Sensitizer (Kayacure DETX from Nippon Kayaku Co., Ltd.) 1 part by mass Air interface side alignment means (X1-3) 0.11 parts by mass Onium salt (X1-4) 1.5 parts by mass Methyl ethyl ketone (solvent) 300 parts by mass

Air interface side alignment means (X1-3)

Composition of the alignment film coating liquid

Modified polyvinyl alcohol, shown below 10 parts by mass Water 371 parts by mass Methanol 119 parts by mass Glutaraldehyde 0.5 parts by mass

Modified polyvinyl alcohol

On a cleaned glass substrate, the coating liquid to form an alignment film was applied using a wire-applied squeegee in an amount of 20 mL/m ² . The coating was dried under warm air at 60°C for 60 seconds and further under warm air at 100°C for 120 seconds, thereby producing a substrate with alignment film. On the surface of the substrate, a coating liquid of the liquid crystal composition (D) was spin-coated at room temperature so that the coating layer thickness was controlled to 1 µm, the coating was aged at 60°C for 1 minute for alignment, and then with light at 50° C was irradiated using a high-pressure mercury lamp with a short-wavelength UV component cutoff for 10 seconds to fix the alignment, thereby forming an optical compensation film. No crystal deposition was observed in the coated film during the period after coating and before heating.

The obtained optical compensation film was observed under a polarizing microscope and was found to exhibit uniform alignment without alignment defect.

Further, Rth measurement of the obtained optical compensation film using AxoScan (Müller Matrix Polarimeter) from Axometrics, Inc. revealed an Rth at 550 nm of -124.8 nm.

[Examples 34 to 41]

Liquid crystal composition coating liquids were each prepared in the same manner as in Example 33 except that Compound (2) to Compound (9) were used instead of Compound (1). Optical compensation films were formed using the respective coating liquids in the same manner as in Example 33. The obtained optical compensation films were observed under a polarizing microscope and were found to exhibit uniform alignment without alignment defect. Further, the Rth measurement value at 550 nm and the thickness of the obtained optical compensation films were summarized as follows. [Table 4] Polymerizable liquid crystal compound of formula (4) Liquid crystal compound of formula (5) Polymerizable liquid crystal compound of formula (6) Re (nm) Film thickness (µm) (15 parts by weight (2 parts by weight) (85 parts by weight) Example 33 connection (1) connection (11) Connection(1-A) -124.1 1.47 Example 34 connection (2) connection (12) Connection(1-A) -126.6 1.47 Example 35 connection (3) connection (13) Connection(1-A) -125.5 1.49 Example 36 connection (4) connection (14) Connection(1-A) -127.7 1.48 Example 37 connection (5) connection (15) Connection(1-A) -127.7 1.47 Example 38 connection (6) connection (16) Connection(1-A) -138.1 1.50 Example 39 connection (7) connection (17) Connection(1-A) -136.5 1.49 Example 40 connection (8) connection (18) Connection(1-A) -119.0 1.47 Example 41 connection (9) connection (19) Connection (1-A) -125.1 1.48

[Examples 75 to 82]

Liquid crystal composition coating liquids were each prepared in the same manner as in Example 33 except that the compounds mentioned in the following table were used instead of Compound (1), Compound (11) and Compound (1-A). Optical compensation films were formed using the respective coating liquids in the same manner as in Example 33. The obtained optical compensation films were observed under a polarizing microscope and were found to exhibit uniform alignment without alignment defect. Further, the Rth measurement value at 550 nm and the thickness of the obtained optical compensation films were summarized as follows. [Table 5] Polymerizable liquid crystal compound of formula (4) Liquid crystal compound of formula (5) Polymerizable liquid crystal compound of formula (6) Re (nm) Film thickness (µm) (15 parts by weight (2 parts by weight) (85 parts by weight) Example 75 Compound (1L) Connection (11L) Connection(1-A) -142.7 1.46 Example 76 Connection (2L) Connection (12L) Connection(1-A) -128.9 1.45 Example 77* Connection (3L) Connection (13L) Connection(1-A) -136.4 1.46 Example 78 Connection (4L) Connection (14L) Connection(1-A) -128.0 1.47 Example 79* Connection (7L) Connection (17L) Connection(1-A) -102.8 1.46 Example 80 Connection (8L) Connection (11M) Connection(1-A) -144.4 1.48 Example 81 Connection (1N) Connection (15M) Connection(1-B) -144, 9 1.49 Example 82 Connection (2N) Connection (14M) Connection(1-A) -143.6 1.47 * Reference example (not covered by the wording of the claims)

Claims (22)

A liquid crystal composition comprising: at least one species of the compound represented by the following formula (4), at least one species of the compound represented by the following formula (5), and at least one species of the compound represented by the following formula (6).

where n1 represents an integer 3 to 6, R ¹¹ represents a hydrogen atom or a methyl group, Z ¹² represents -CO- or -CO-CH=CH-, R ¹² represents a hydrogen atom, a straight-chain alkyl group with 1 to 4 carbon atoms, a methoxy group , an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, an allyloxy group or a structure represented by the following formula (1-3).

wherein Z ¹³ represents -CO- or -CO-CH=CH-, Z ¹⁴ represents -CO- or -CH=CH-CO-, each of R ¹³ and R ¹⁴ independently represents a hydrogen atom, a straight chain alkyl group with 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, an allyloxy group or a structure represented by the following formula (1-3),

wherein each of n2 and n3 independently represents an integer from 3 to 6 and each of R ¹⁵ and R ¹⁶ independently represents a hydrogen atom or a methyl group, -Z ⁵¹ -T-Sp-P Formula (1-3) where P represents an acrylic group or a methacrylic group, Z ⁵¹ represents -COO-, T represents a 1,4-phenylene group and Sp represents an optionally substituted divalent aliphatic group having 2 to 6 carbon atoms, a CH ₂ group or two or more non-adjacent ones CH ₂ groups in the aliphatic group can be replaced by -O-, -OCO-, -COO- or -OCOO-. Liquid crystal composition according to Claim 1 , wherein at least two of R ¹² , R ¹³ and R ¹⁴ represent the same substituent. Liquid crystal composition according to Claim 1 or 2 , where n ¹ 4. Liquid crystal composition according to any one of Claims 1 until 3 , wherein each of R ¹¹ , R ¹⁵ and R ¹⁶ represents a hydrogen atom. Liquid crystal composition according to any one of Claims 1 until 4 , wherein each of Z ¹² , Z ¹³ and Z ¹⁴ represents -CO-. Liquid crystal composition according to any one of Claims 1 until 5 , wherein each of R ¹² , R ¹³ and R ¹⁴ independently represents a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenyl group, an acryloylamino group, a methacryloylamino group, an allyloxy group or a structure represented by the following formula (1-3). represents: -Z ⁵¹ -T-Sp-P Formula (1-3) where P represents an acrylic group or a methacrylic group, Z ⁵¹ represents -COO-, T represents a 1,4-phenylene group and Sp represents an optionally substituted divalent aliphatic group having 2 to 6 carbon atoms, a CH ₂ group or two or more non-adjacent ones CH ₂ groups in the aliphatic group can be replaced by -O-, -OCO-, -COO- or -OCOO-. Liquid crystal composition according to any one of Claims 1 until 6 , wherein each of R ¹² , R ¹³ and R ¹⁴ represents a phenyl group. Liquid crystal composition according to any one of Claims 1 until 7 , which contains 3 to 50 mass% of the compound represented by formula (4) and 0.01 to 10 mass% of the compound represented by formula (5) based on the compound represented by formula (6). Liquid crystal composition according to any one of Claims 1 until 8th , which contains at least one species of a polymerization initiator. Liquid crystal composition according to any one of Claims 1 until 9 , which contains at least one species of a chiral compound. A method of producing a polymeric material comprising polymerizing one in any of Claims 1 until 10 described liquid crystal composition. Method for producing a polymer material according to Claim 11 , wherein polymerization is achieved by irradiation with ultraviolet radiation. Polymer material obtainable by polymerizing the in any of Claims 1 until 10 described liquid crystal composition. Use of the liquid crystal composition according to any one of Claims 1 until 10 for producing a film containing at least one species of polymer material obtainable by polymerizing the liquid crystal composition. Use of the liquid crystal composition according to any one of Claims 1 until 10 for producing a film comprising an optically anisotropic layer configured by fixing an orientation of the liquid crystal compounds contained in the liquid crystal composition. Use according to Claim 15 , wherein the optically anisotropic layer is configured by fixing a cholesteric orientation of the liquid crystal compounds. Use according to Claim 16 , where the film has a selective reflection property. Use according to Claim 16 or 17 , wherein the film has a selective reflection property in the infrared wavelength range. Use according to Claim 15 , wherein the optically anisotropic layer is configured by fixing a homogeneous alignment of the liquid crystal compounds. Use according to Claim 15 , wherein the optically anisotropic layer is configured by fixing a homeotropic orientation of the liquid crystal compounds. Use of the liquid crystal composition according to any one of Claims 1 until 10 for producing a polarizing plate comprising a film and a polarizing film, the film comprising an optically anisotropic layer configured by fixing a homogeneous or homeotropic orientation of the liquid crystal compounds contained in the liquid crystal composition. Use of the liquid crystal composition according to any one of Claims 1 until 10 for producing a liquid crystal display device comprising a polarizing plate comprising a film and a polarizing film, the film comprising an optically anisotropic layer configured by fixing a homogeneous or homeotropic orientation of the liquid crystal compounds contained in the liquid crystal composition.